DE2356213A1 - NEW PREPOLYMERS INCLUDING KETIMING GROUPS - Google Patents

Description

235: 621

SCHERING AG
Patent department

New prepolymers containing ketinine groups

Addendum to patent ..................

(Patent application P. ...)

Subject of the main patent ..c (patent application

P / V.r.%. R..o. * ....) are new prepolymers containing enamine groups, Manufactured by reacting monoenamines containing free hydroxyl groups with polyisocyanates.

Special embodiments of the main patent are characterized in that the monoenamine containing free hydroxyl groups is a monoenamine based on 1- (2-hydroxyethyl) piperazine and that the polyisocyanates are addition products of polypropylene glycols and excess diisocyanates. ._ "'...

Subject of the main patent (patent application

P.) is also a process for producing the

Enamine group-containing prepolymers, which is characterized in that at least one secondary amino group and one aliphatic hydroxyl group-bearing compounds in

1. First stage with aliphatic aldehydes or cyclic ketones reacted, the reaction being catalyzed, if appropriate, by acids, if appropriate by supplying heat

or cooling, with or without solvent, carried out - - and with the corresponding reaction ^ water and the excess carbonyl compounds removed, and that one

2. the compounds obtained under 1. in the second stage with

■ converts such amounts of polyisocyanates that the water

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SCHERING AG -Z- 2 3 5 6? 1

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substance of which hydroxyl groups are equivalent *

There was now a further formation containing the new enamine groups Prepolymers according to patent ........... (patent application

P) towards new containing ketimino groups

Prepolymers made by reacting free hydroxyl groups containing mono-ketimines with polyisocyanates - found.

Another embodiment of the prepolymers according to the invention is characterized in that the polyisocyanates are aliphatic polyisocyanates.

A further embodiment of the prepolymers according to the invention is characterized in that the polyisocyanates are addition products from polypropylene glycols and excess diisocyanates are,

The invention also relates to a process for the preparation of the prepolymers containing ketimine groups, which is characterized in that is that you have at least one primary amino group and one compounds bearing aliphatic hydroxyl groups in

1. Reacts the first stage with aliphatic or cyclic ketones, the reaction optionally being carried out Acids catalyzed, if appropriate by supplying heat or cooling, with or without a solvent, carried out and wherein the corresponding water of reaction and the excess carbonyl compounds are removed, and that one

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2. Reacts the compounds obtained under 1. in the second stage with such amounts of polyisocyanates that the Viasserstoff the hydroxyl groups are equivalent »

Another form of process for the preparation of prepolymers containing ketimine groups is characterized in that the polyisocyanates are addition products of polypropylene glycols and excess diisocyanates.

It was not previously known that ketimines, the hydroxyl groups contained, while maintaining the ketimine structure in its original form. Isocyanates with the formation of urethane groups let add. .

Rather, it is described in the literature that ketimines with isocyanates can react with formation of cyclic addition products or products containing amide or urea groups (K. Hiirada, Makromol. Chem. 132, 295-304, 1970).

The ketimines according to the invention are prepared by adding an excess of the carbonyl component to the primary amines and, after adding a suitable solvent (toluene, benzene), heating them under nitrogen on a water separator until the water separation has ended. In some cases, the carbonyl can serve as a tractor itself.

Distillation of the ketimine is advantageous. However, the crude product can also be used directly after the excess carbonyl component and the solvent have been removed.

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The carbonyl components are, in particular, aliphatic and cyclic ones Ketones suitable »Examples of ketones that can be used with advantage for the preparation of ketimines are;

Cyclopentanone, trimethylcyclopentanone, cyclohexanone, trimethylcyclohexanone and other substituted cyclohexanones and cyclopentanones as well as methyl isobutyl ketone, methyl ethyl ketone, diethyl ketone, diisopropyl ketone etc.

For the addition of the Ketime containing hydroxyl groups, pre-adducts from polypropylene glycols and excess aliphatic diisocyanates are used »

The underlying polypropylene glycols are linear or branched products with an average molecular weight between 500 and 10,000 «,

It is advantageous to use aliphatic diisocyanates with isocyanate groups of different reactivity, as this results in chain lengthening is avoided.

Such diisocyanates are, for example, isophorone diisocyanate and trimethylhexamethylene diisocyanate. In cases where chain extension is desired, hexamethylene diisocyanate, 1-methyl-2,4-diisocyanatocyclohexane or 4,4 ^I -diisocyanatodicyclohexylmeihan can also be used.

The diisocyanates are preferably in a ratio of the isocyanate to Hydroxyl groups of 1.8-2.2 added. In general, it makes sense to mix the components with cooling at 0-30 C and

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a catalyst such as B. organic tin compounds or add tertiary amines. Then the mixture is so long heated to elevated temperatures of preferably 50-100 C until " the analytically "determined isocyanate content corresponds to the calculated value is equivalent to.

The ketimines containing hydroxyl groups become the isocyanate pre-adduct preferably in a ratio of NCO / OH equal to 1. the Mixing must be done with vigorous stirring and, if necessary, under Cooling can be done at temperatures of 0-30C «It will take so long stirred until free isocyanate can no longer be detected by infrared spectroscopy.

The ketimine adducts according to the invention can be used as amine-splitting compounds, for. Use B ₀ for moisture-curing polyurethane compounds.

For this purpose they are masked with aromatic polyisocyanates mixed in an approximately stoichiometric ratio.

As masked polyisocyanates come for this. B. Adducts / from Trimethylolpropane and 2,4-toluene diisocyanate in a molar ratio 1: 3 in question, whereby the free isocyanate groups can be capped with phenol.

Adducts of polypropylene glycols and 2,4-toluene diisocyanate can also be used with nonylphenol-capped residual isocyanate groups can be used.

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example 1

a) In a 1 liter di-healing flask with water separator and stirrer 91.5 g of ethanolamine, 225 g of methyl isobutyl ketone and 100 ml of benzene presented «

It is refluxed until the calculated amount of water has separated out.

Excess ketone and solvent are then drawn off and the residue is distilled in vacuo. Bp 53 ° C / 0.5 mm

Analysis ;

CHN

calculated 67% 11.9 % 9.8 %

found 66.8 % 12.1 % 9.8 %

There is a strong K & timin band in the infrared spectrum

-1
1655 cm

Formula of the reaction product:

/ ^CH 3
HO-CH ₂ -CH ₂ -N = C / 3

CH ₀ -CH _x

^CH 3

b) A mixture of 5040 g of a trifunctional polypropylene glycol the OH number is 35.6 and 711 g of isophorone diisocyanate with 5.7 g of dibutyltin dilaurate and for 3 hours at

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Stirred at 75 C under nitrogen * The reaction product has an isocyanate content of 2.2 percent by weight, corresponding to an equivalent weight of 1914 _O

c) 1000 g of the isocyanate end groups prepared under b) Prepolymers are cooled with 74.83 g of the under a) prepared hydroxyl-containing ketimine ver. sets «While stirring vigorously, we ensure that the temperature does not rise above 30 C«

After a stirring time of 4-5 hours, free isocyanate can no longer be detected in the infrared spectrum. The ketimine gang is against it preserved. The product has an equivalent weight of 2057.

Example 2 ₀

a) A mixture of 105 g DiglykoTamine and 150 g cyclohexanone 100 ml of benzene are added and the water separator is used for 4 hours heated ", 17.6 g of water separate".

The excess ketone and the solvent are drawn off and the residue is distilled in vacuo _, bp 103 ° C./0.2 mm

Analysis; ·

C. H N

calculated 64.8% 10.3 % 7.6%

found 64.8 % 10.3 % 8.0 %

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The reaction product has the formula
HO-CH-CH ₂ -O-CH ₂ -CH ₂ -N =:

b) 1000 g of the isocyanate end groups prepared under 1 b) Prepolymers are made with cooling and vigorous stirring mixed with 96.6 g of the ketimine prepared under 2 a).

The temperature is kept below 30 ° C. during the reaction. After 5 hours of stirring, no infrared spectrum can be seen detect more free isocyanate. The product has an equivalent weight of 2100.

Example 3

a) 324 g of diglycolamine are mixed with 300.5 g of methyl isohutyl ketone and 300 ml of benzene are added.

The mixture is heated on a water separator under nitrogen until the water separation has ended. The solvent is drawn off and the residue is distilled in vacuo.

The reaction product has the formula:

' PH HO-CH-CH ₂ -O-CH-CH ₀ -N = C y ^Π 3

CH ₂ -CH

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h) 1000 g of the isocyanate end groups prepared under 1 b) 97.8 g of the ketimine prepared under 3 a) are added to prepolymers with stirring and cooling.

After stirring for 4 hours, infrared spectroscopy can be used no more free isocyanate can be detected .. The product .has a 2012 equivalent weight.

Example 4

a) 117 g of 1,6-hexanolamine are mixed with 150 g of cyclohexanone and 100 ml Benzene is heated on the water separator until no more water of reaction is formed. The reaction is after Finished about 6 hours

The excess ketone and benzene are removed in vacuo and the residue is distilled in vacuo. 153 ° C / 0.8 mm.

Analysis;

C H N

calculated 73.0 % 11.7 % 7.1 %

found 73.5 % . 11.7 % 6.8%

The infrared spectrum shows a strong C = N band at 1660 cm.

The reaction product has the formula
H0- (CH _{2) 6} -N =

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b) 1536 g of a branched polypropylene glycol with an OH number 35.6 v / earth with 221 g of isopharone diisocyanate and 1.8 g of dibutyltin dilaurate offset.

The reaction mixture is heated to 75 ° C. and kept at this temperature for 2.5 hours with thorough stirring. The reaction product has an isocyanate content of 2.39 %.

c) prepolyning 1000 g of the prepared in example 4 b) Isocyanates are mixed with 112.2 g of the ketimine containing hydroxyl groups prepared in Example 4 a) at room temperature stirred. After the mixture has stood for about 12 hours, no free can be seen in the infrared spectrum Detect more isocyanate.

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Claims (5)

SCHERING AG patent department P α t e η t σ η s ρ r ü c h e 1.) Further development of the new prepolymers containing enamine groups according to patent .......... ₄ . (Patent application P. PifAfSÄA.) In the direction of new prepolymers containing ketimine groups, prepared by reacting monoketimines containing free hydroxyl groups with polyisocyanates «, 2.) New prepolymers containing ketimine groups according to claim 1, characterized in that the polyisocyanates are aliphatic polyisocyanates. 3.) New prepolymers containing ketimine groups according to claim 1, characterized in that the polyisocyanates are addition products of polypropylene glycols and excess diisocyanates are. 4.) Process for the preparation of prepolymers containing ketimine groups, characterized in that there is at least one primary amino group and one aliphatic hydroxyl group load-bearing connections in 1. first stage with aliphatic or cyclic ketones ^ reacted, the reaction being catalyzed, if appropriate, by acids, if appropriate by supplying heat or cooling, with or without a solvent, and the corresponding water of reaction and the excess carbonyl compounds are removed, and that 50 9820/0931 -2- SCHERING AG Patent Department / 9 2 · the compounds obtained under 1 «in the second stage Reacts with such amounts of polyisocyanates that the Hydrogen of hydroxyl groups are equivalent. 5.) Process according to claim 4, characterized in that the polyisocyanates are addition products of polypropylene glycols and excess diisocyanates. 509820/0931