DE102007039501A1 - New polymerisable isocyanate and polymers containing this isocyanate - Google Patents

Abstract

The invention relates to a novel alkenyl isocyanate characterized by the chemical formula $ F1. This compound is obtained by reacting isophorone diisocyanate with N- (t-butyl) aminoethyl methacrylate. The new compound is particularly suitable for the preparation of homopolymers and copolymers which can be used in particular as Lackharzpolymerisate. The polymers are distinguished by good solubility in various solvents and by good dispersibility in oligomeric, low molecular weight and high molecular weight polymers.

Description

The The invention relates to a novel alkenyl isocyanate, d. H. a connection, which has an ethylenic double bond and an isocyanate function, a method for producing the same and the use of the same Compound in the manufacture and processing of polymers.

alkenyl isocyanates have been known for some time already.

So be in the U.S. Patent 2,958,704 so-called monoalkenyl urethane monoisocyanates, ie compounds which have a polymerizable double bond and a reactive isocyanate function, wherein the part of the compound having the isocyanate group is connected to the part having the ethylenic double bond via a urethane bond. The compounds described therein can be used for homopolymerization or co-polymerization.

In the EP 0343476 A2 Alkenylisocyanate are described which are used to build compounds which have an ethylenic double bond and a urea function.

Finally, in the US PS 4670506 describe a series of carbamoyloxyethyl methacrylates which have an isocyanate function. According to the teaching of this patent, these compounds are suitable to react with polyvinyl alcohol to form a urethane. The resulting polymers can then be crosslinked due to the presence of the ethylenically unsaturated double bond. The new compound according to the invention is not disclosed there.

Even though in this specification in the examples a whole series of alkenyl isocyanates There is still a need for such compounds with improved properties, after a simple and economical Process for the preparation thereof and for corresponding alkenyl isocyanates, which is particularly advantageous in processing and manufacturing of polymers, in particular of corresponding plastics and paints to use.

task The invention therefore provides a novel alkenyl isocyanate to ask, compared to the known alkenyl isocyanates characterized by good properties that are easy and reproducible and can be produced economically without the use a catalyst can be generated and used and that too in the production and processing of polymers without catalysts can continue to be used and in particular by good Solubilities in various solvents as well as characterized by a good dispersibility in polymers Both in polymers, as oligomers, as low molecular weight as well as high molecular weight polymers.

task The invention further provides a corresponding alkenyl isocyanate to provide, with the tailor made Plastics and paints can be produced.

This object is achieved by an alkenyl isocyanate having the chemical formula

These Compound is also 2- (N- (tert-butyl) {[(3-isocyanato-1,5,5-trimethylcyclohexyl) methyl] amino} carbonylamino) ethyl methacrylate called.

object the invention is also a manufacturing method of this compound, which is characterized in that isophorone diisocyanate with N- (t-butyl) aminoethyl methacrylate is reacted. Preferably that gets Diisocyanate with the N- (t-butyl) -aminoethyl methacrylate in equimolar Ratios to the reaction.

The Reaction can take place in an inert solvent.

When Solvents are in particular aprotic solvents used.

One Another object of the invention is the use of the invention Alkenyl isocyanate for the preparation of polymers and the polymers itself, in particular of Lackharzpolymerisate.

These can be used in the automotive sector (clearcoats, refinishes), in printing plates, in electronics (solder resists, photoresists) and used in building protection. Also is a use possible in adhesives.

One Another object of the invention is an isocyanate-containing polymer, which is characterized in that it consists of 99 to 50 wt .-% Monomers of the (meth) acrylic acid ester type or styrene and of 1 to 50% by weight of 2- (N- (tert-butyl) {[(3-isocyanato-1,5,5-trimethylcyclohexyl) methyl] amino} carbonylamino) ethyl methacrylate is constructed.

Compared to other alkenyl isocyanates, the compound according to the invention has improved solubility in a variety of solvents, especially those used in paint manufacture. So z. B. the compound of the invention in a mixture of butyl acrylate and methyl methacrylate to 30%, whereas in Example 12 of the US 4,670,506 described compound which is obtained by the reaction of 2,4-toluene diisocyanate with t-butylaminoethyl methacrylate dissolves only 10%. This makes it possible to produce valuable starting components for the paint production.

Especially It is advantageous that the preparation of the inventive Alkenylisocyanats possible without the use of catalysts is. This also brings advantages in use for production of polymers, plastics and paints, as catalyst residues in end products very often disadvantageous.

The using the alkenyl isocyanate of the invention Lackharzpolymerisate produced tend to lesser when weathered Discoloration and have very good practical pendulum hardnesses.

The inventive compound is suitable for this means Polymerization first to produce homopolymers.

The Compound can also be used as a comonomer. The corresponding Isocyanate group-containing compounds can then subsequently z. B. crosslinked by urethanization agents such as 1,4-butanediol become. Likewise, moisture-crosslinking polymers can be produced, used as adhesives for metals, glass and plastics can be.

The Polymers according to the invention can also reacted with blocking agents for the isocyanate group for example, to a subsequent cross-linking reaction at a higher temperature. Can do this known compounds such. For example, methyl ethyl ketoxime be used. Thus, self-curing Einkomponentenlackharzsysteme being constructed.

The The invention is further illustrated by the following examples:

example 1

In 166.7 g of isophorone diisocyanate are added to a reaction vessel and 0.153 g of 2,6-di- (tert-butyl) -4-methylphenol as a polymerization inhibitor submitted. Then N- (tert-butyl) aminoethyl methacrylate (138.9 g) within 2 hours. The bottom temperature is thereby kept at a maximum temperature of 30 ° C. After completion The mixture is added for a further 3 hours at a maximum of 30 ° C held. It is stirred. The end product is a highly viscous yellowish oil, namely 444 g, which corresponds 99% of theory. According to NMR spectroscopy, the product corresponds to the Structure 2- (N- (tert-butyl) {[(3-isocyanato-1,5,5-trimethylcyclohexyl) methyl] amino} carbonylamino) ethyl methacrylate.

Example 2 (Inventive Polymer)

Preparation of a solution polymer with 2- (N- (tert-butyl) {[(3-isocyanato-1,5,5-trimethylcyclohexyl) methyl] amino} carbonylamino) ethyl methacrylate.

you place 100 g of methyl ethyl ketone (MEK) under nitrogen in the reaction vessel and heated to 80 ° C internal temperature. Within 4 hours While stirring, a mixture of 30.7 g of 2,2'-azobis- (2,4-dimethylvaleronitrile) is metered in, 82.3 g isobornyl methacrylate, 115 g methyl methacrylate (MMA), 173 g of butyl acrylate, 7.4 g of dodecyl mercaptan and 41 g of 2- (N- (tert-butyl) {[(3-isocyanato-1,5,5-trimethylcyclohexyl) methyl] amino} carbonylamino) ethyl methacrylate added. After the addition, the mixture is left at 80 ° C. for 0.5 h afterreact. Another 0.4 g of 2,2'-azobis (2,4-dimethylvaleronitrile) are added. in 10 g of MEK and allowed to 2 h at 80 ° C. afterreact. Then add 40 g of MEK and leave Cool to room temperature while stirring.

This gives a 75% solution of the polymer in MEK with the following composition:
20% isobornyl methacrylate
28% MMA
42% butyl acrylate
10% 2- (N- (tert-butyl) {[(3-isocyanato-1,5,5-trimethylcyclohexyl) methyl] amino} carbonylamino) ethyl methacrylate

Example 3 (comparison, not according to the invention)

Preparation of a solution polymer with 2 - {[N- (3-isocyanato-4-methylphenyl) carbamoyl] (tert-butyl) amino} ethyl methacrylate.

you put 50 g of dry n-butyl propionate under nitrogen in the reaction vessel and heated to 80 ° C internal temperature. Within 4 hours While stirring, a mixture of 16.3 g of 2,2'-azobis- (2,4-dimethylvaleronitrile) is metered in, 41.2 g isobornyl methacrylate, 57.6 g methyl methacrylate (MMA), 86.4 g of butyl acrylate, 3.7 g of dodecyl mercaptan and 20.6 g of 2 - {[N- (3-isocyanato-4-methylphenyl) carbamoyl] (tert-butyl) amino} ethyl methacrylate added. After the addition, the mixture is left at 80 ° C. for 0.5 h afterreact. Another 0.21 g of 2,2'-azobis (2,4-dimethylvaleronitrile) is added. in 5 g of n-butyl propionate and allowed to 2 h at 80 ° C. afterreact. Subsequently, 40 g of n-butyl propionate are added and allowed to stir with stirring to room temperature cooling down.

This gives a 75% solution of the polymer in n-butyl propionate having the following composition:
20% isobornyl methacrylate
28% MMA
42% butyl acrylate
10% 2 - {[N- (3-isocyanato-4-methylphenyl) carbamoyl] (tert-butyl) amino} ethyl methacrylate

Example 4 Chemical resistance of films of the polymers of Example 2 and Example 3

Production of the films:

49.4 g of a polymer solution diluted to 60% with methyl ethyl ketone from Example 2 or Example 3 is treated with 0.59 g of a 60% solution of 1,4-butanediol in methyl ethyl ketone and 0.35 g of a 0.01% Solution of dibutyltin dilaurate in the solvent mixture Solvesso 100: n-butyl acetate = 2: 1 mixed and on metal plates in 25 minutes at 145 ° C to 30 microns thick films networked.

Resistance test:

• a) Testmedium 5%ige Natronlauge Film aus Polymer nach Beispiel 2: Oberfläche weist Risse und beginnende Durchätzung auf. Film aus Polymer nach Beispiel 3: Oberfläche ist durchgeätzt.
• b) Testmedium 20%ige Salzsäure Film aus Polymer nach Beispiel 2: Oberfläche ist matt und weich. Eine Verfärbung ist erkennbar. Film aus Polymer nach Beispiel 3: Oberfläche weist Risse und beginnende Durchätzung auf.

One drop of each medium is applied to a sample of the crosslinked film. The substance is left on the film at 80 ° C. for 30 minutes, then the surface of the film is rinsed with deionized water and dried with blotting paper. The film surface is visually assessed.

• a) Test medium 5% sodium hydroxide film of polymer according to Example 2: surface has cracks and incipient etching. Film of polymer according to Example 3: surface is etched through.
• b) Test medium 20% hydrochloric acid film of polymer according to Example 2: surface is dull and soft. A discoloration is recognizable. Polymer film according to Example 3: surface has cracks and incipient etching.

It turns out that the polymer according to Example 3 a reduced chemical resistance in the United has the same polymer according to Example 2.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - US 2958704 [0003]
• EP 0343476 A2 [0004]
• US 4670506 [0005, 0017]

Claims (7)

Alkenyl isocyanate characterized by the chemical formula

Process for the preparation of the compound according to claim 1, characterized in that isophorone diisocyanate with N- (t-butyl) aminoethyl methacrylate implements. Method according to claim 2, characterized in that that is the isocyanate with the N- (t-butyl) aminoethyl methacrylate in equimolar ratios to the reaction. Method according to claim 2 or 3, characterized that the reaction is carried out in an inert solvent becomes. Method according to claim 4, characterized in that that as solvent, an aprotic solvent used. Isocyanate-containing polymer, characterized from 99 to 50% by weight of (meth) acrylic ester type monomers or styrene and from 1 to 50 wt .-% 2- (N- (tert-butyl) {[(3-isocyanato-1,5,5-trimethylcyclohexyl) methyl] amino} carbonylamino) ethyl methacrylate is constructed. Use of the alkenyl isocyanate according to claim 1 and the alkenyl isocyanate prepared by one of the methods according to at least one of claims 2 to 5 for the preparation and processing of polymers, in particular lacquer resin polymers.