CS208984B1 - Alkanol aminecarbamate lengthener for thermoreactive systems - Google Patents

Abstract

This is the use of the extender's thermoreactive systems suitable for coating, coating, connecting layers, or self-supporting films. Elastic polyurethane layers can be used preferably applied in the manufacture of leather skins for various purposes, especially in shoemaking, upholstery, haberdashery and clothing. The extender according to the invention comprises alkanolamines aliphatic, cycloaliphatic or aromatic and one or more amino groups or more hydroxyl groups whose amino groups are present they are blocked by carbon dioxide and are a mixture of at least two alkanolamines with amino groups blocked by carbon dioxide.

Description

The invention relates to alkanolamine carbamate extenders for thermoreactive systems which are suitable for coating, coating, coating compositions _; connecting layers or self-supporting layers and foils. -i <', /

The use of polyamines to extend the chains or polyurethanes is well known. Because of the high reactivity of polyamines with isocyanate groups: polyamines cannot be used in solvent-free systems unless one of the reactive groups is blocked. It is known that shelf life adj listovaných systems containing bloko- _f Vane prepolymers and unblocked polyamine is problematic, since due to the homogeneous system of recovering balance! - isocyanate group + block. reagent block. According to type I of the blocking agent, the isocyanate group ¹ agent also cures more slowly. An unpleasant consequence of this reaction is the increasing viscosity of the mixture, which over time becomes unsuitable for processing. ;

The disadvantages of varying the viscosity of the finished mixture can be solved by using a system comprising a non-blocked prepolymer and a carbon dioxide-blocking polyamine extender-carbapiate. Since J polyamine carbamate is γ of the prepolymer insoluble i and forms a heterogeneous mixture, these adjusted mixtures in the hermetically sealed areas can be stored indefinitely under normal storage conditions. However, their disadvantage is that the preparation of β-carbamates must be carried out separately

By step a to achieve smooth surfaces by heat;

. hardened flat formations must be used; mixtures of polyamines or polyamine carbamates having a broader particle distribution. at

When polyamino carbamates are prepared directly in the environment in which they are used, e.g.

! In the preparation of the mixture, there is an enormous increase in the viscosity of the mixture, which indicates that the prepolymer has been partially prolonged. ^{: 1} . '| [Finally, polyamine carbamates themselves, J

2 ^y , if prepared in very fine form,

They also enhance the viscosity of the coating composition in an ethereal manner, although any elongation of the prepolymer is prevented by physical or chemical intervention. It is possible to prepare polyamino carbamates in polyols and to use this mixture as such so that there is no need to count on ¹ viscosity increase for application, in which case the advantage of simple one-component handling, mixing and complex dosing and mixing needs to be avoided. equipment. Indeed, in this case, it is also necessary to take into account the need to use only polyamines of low molecular weight, since polyamines of higher molecular weight give very bulky precipitates. >

The disadvantages of polyamine protectors eliminate the extenders for the reactive system of the invention, which consists in containing alkanolamines of aliphatic, cycloaliphatic or aromatic series with one or more | amino groups and one or more hydroxyl groups whose amino groups are blocking; carbon dioxide.

Since multi-functional amino alcohols can be advantageously used as extenders, crosslinked materials having excellent physico-mechanical properties can be obtained after curing of the deposits. Multifunctional alkanolamines, converted by the blocking of amino groups with carbon dioxide to alkanolaminarmabates, also exhibit different reactivities of primary and secondary amine groups in thermal deblocks, influenced not only by different decomposition temperatures depending on functionality but also by their position in the aminoalcohol molecule.

Another advantage of some alkanolaminocarbamas; The idea is that they do not form suspensions in the polyols, but emulsions that pass into solution when the polyol is converted to a prepolymer. If it was caused by the binding of carbamate molecules; alkanolamines to the prepolymer molecules via OH! initial aminoalcohol groups e.g. 'i 0 = C = N? h ^ NH.CoI.OC .nhÍ 3 XY where j: .....' ..... ...... ~~ 7 ⁷ i

I = the remainder of the aliphatic, cyclicaliphatic or aromatic alkanolamine

II = residue of any other alkanolamine used from the aliphatic, cycloaliphatic or aromatic series x = number of carbon atoms in alkanolamines I y = number of hydrogen atoms in alkanolamines I z = number of carbon atoms in alkanolamines Π v = number of carbon atoms in alkanolamines II; the reactive component of the polyurethane composition would actually be monolithic, but the chain of the prepolymer would be at least doubled. However, this contradicts the fact that the viscosity of the adjusted mixture is low, generally only slightly higher than

II.

OOCNH. C H ol C0NH ~ ** N. ·· C = 0

ZV i _r .

the viscosity of the prepolymer itself and also disagree with the results of analyzes which show that in the finished thermoreactive mixture one hydroxyl group is free. In this case it must be the hydroxyl group of the alkanolamine carbamate, which is sterically protected from the isocyanate J group so that it is completely inactive, as indicated by the constant viscosities measured during storage. and

Microscopic observations of the adjusted compositions show that the reaction of the isocyanates with the polyols also creates an environment in which the alkanolamine carbamate is completely or to a greater extent soluble, since the dispersive nature of the mixture is evidently disappearing. This further increases the shelf life of the compositions which do not threaten the sedimentation of the dispersed particles or their agglomeration.

The alkanolaminocarbamates prepared as the additive are mostly viscous, honey-like substances and can be easily mixed into epoxy resins, where they can be incorporated into the mixtures, cured; heat.

Adducts of alkanolaminocarbamates with isocyanate-terminated prepolymers give, after curing, smooth deposits, the formation of which is influenced by a gradual increase in viscosity over a wide temperature range, as they degrade according to the functionality of the amino group and finally the OH-alkanol reacts with the prepolymer.

The advantages of both polyamino carbamate and alkanolamine carbamate extenders are combined by the extender, which is a mixture thereof. The polyamine component provides excellent strength properties of the cured formations, while the alkanolamine component contributes to the formation of completely smooth surface deposits.

The extender according to the invention can be prepared by adding carbon dioxide in anhydrous medium to the amino alcohols of the aliphatic, cycloaliphatic and aromatic series of the type

HO - / c /

AND

R, x

wherein R 1, R ₂ are H, CH ₃ , C ₂ H ₅ , C ₃ H ₈ , C ₄ H _n

-O · -'Ό '

R ₃ is H, CH ₃ , G ₁ H ₃ , -CH ₂ OH R _{4 is} H, CH ₃ , -CH 2, 3 bx = 2-6, y = 2.3 \ z = 2-4, the amino groups of which are blocked with carbon dioxide, preferably to aliphatic polyaminal alcohols such as ethanolamine, diethanolamine, aminoethylisopropanolamine

H ₂ NC ₂ H ₄ NH.CH ₂ CH CH ₃

OH aminoethylethanolamine H ₂ N C ₃ H ₄ NHC ₂ H ₄ OH but also for aromatic ethylenediiminodi (o-cresol)

The extender according to the invention can advantageously be used as one of the reactants in particular in polyueratan systems.

The thermoreactive systems containing the extender according to the invention can be advantageously used in the preparation of cast, coated or dipped layers which can be used after curing as castings, protective insulating or covering hard and soft coatings, bonding or self-supporting layers or laminated layers for both hard and soft foam thermal and electrical insulation materials, as filling materials for self-supporting metal, wood and plastic constructions, in insulation technology for lining of refrigerators or hot and cold water storage tanks. The elastic polyurethane layers can be advantageously applied in the manufacture of plastic skins for various purposes, in particular in the shoe, upholstery, haberdashery and apparel industries.

The following examples serve to illustrate the invention further:

Example 1

30 parts by weight of diethanolamine having a molecular weight of 105.14 were stirred into 100 parts by weight of anhydrous methanol and bubbled through carbon dioxide in a stirred vessel to form a white crystalline carbamate precipitate with a molecular weight of 127.14. After the alkaline reaction has disappeared, the mixture is filtered, washed with anhydrous methanol, dried at 40 ° C and passed through a sieve with a mesh size of 0.02 mm.

To 100 parts by weight of a prepolymer prepared from polyoxipropylene glycol and diphenylmethane diisocyanate containing 3.3 isocyanate groups are added 3.33 parts by weight of diethanolamine carbamate, 0.01 parts by weight of dibutyltin dilaurate, 20 parts by weight of finely precipitated calcium carbonate, 1.5 parts by weight of silane; Equine surfactants and 0,5% by weight parts of a pigment from the group of phthalocyanine dyes. After thorough dispersion of all components, it is mixed on release paper and cured for 4 minutes at 160 ° C to give a non-sticky, smooth flat formation having a tensile strength of 2.4 MPa, an elongation of 295% and a tear strength of 5, 8 N / mm.

Example2

To 200 parts by weight of 2000 polyoxipropylene glycol were added 7 parts by weight of aminoethylethanolamine and 1 part by weight of silicone surfactant. While stirring, the mixture is bubbled through with carbon dioxide dried through 4A molecular sieve until the reaction to the amino groups is negative. A mixture of 17 parts by weight of toluene diisocyanate and 25.6 parts by weight of toluene diisocyanate is then added to the mixture.

Aniline isocyanates having an addition of 0.01 part by weight of stannous octoate and 0.1 part by weight of methyl morpholine. The mixture was stirred for 20 minutes and then allowed to react at 30 ° C for 12 hours. >

10 10 parts by weight of finely precipitated barium sulphate, 7 parts by weight of finely ground kaolin and 3 parts by weight of talc sieved through a 0.06 mm sieve are added to the mixture. After adding 2 parts by weight of fine powdered pigment, the mixture is stirred at 150 rpm for 30 minutes and filled into containers under which the lid is filled with dry nitrogen before closing. The mixture having a viscosity of 32.5 Pas at 30 ° C had a viscosity of 32.3 Pas at 30 ° C in 23 days.

The mixture was poured in a thin layer onto a thin-walled molded metal casting, which after heating was heated to 160 ° C with a flow of heat transfer medium from the inside. The coating cured within 2 minutes to give an accurate copy of the fine details of the mold after removal from the mold, the outer surface being smooth and shiny, the shaped body itself being slightly porous with regular: open pore size, non-sticky and elastic. j

Example 3

The aminoethyl isopropanolaminocarbamate was prepared as described in Example 1 and, after removal of the methanol, dried under a vacuum of 130 Pa at 30 ° C for 12 hours. A honey-like viscous liquid is obtained with an H equivalent of 48.7.

Weigh 100 parts by weight of epoxy resin with an epoxy equivalent weight of 190, and add 25.6 parts by weight of aminoethyl isopropanolamine carbamate at room temperature. The mixture is poured into a cavity in an aluminum mold heated to 160 ° C into which the parts to be cast are fixed. After curing, which occurred within 20 minutes, a rigid, hard foamed block having a Martens shape stability of 120 ° C and a density of 763 kg / m ^{3 was obtained} .

Example 4

A mixture of 21 parts by weight of aminopvopanol and 10.5 parts by weight of diethanolamine is added to 1000 parts by weight of a 4: T polyoxipropylene lenglycol / polybutylene adipate mixture having an average molecular weight of 1800. After addition of the silicone surfactant in an amount of up to 10 parts by weight, carbon dioxide dried by passing through silica gel and phosphorus pentoxide are also introduced into the mixture with stirring. The introduction is carried out with stirring at 200 rpm fat until the reaction to the amino groups is neutral. The resulting mixture of alkanolaminocarbamates in the polyols is cooled to 10 ° C and 195 parts by weight of toluene diisocyanate are added, which are left to react in the cold for 1/2 hour. Then, a mixed catalyst consisting of 500 parts by weight of N-methylmorphine, 500 parts by weight, is added. % by weight of dimethylethanolamine and 200 parts by weight of triethylenediamine, in an amount of 12 parts by weight, and left to react at room temperature for 48 hours.

The mixture thus prepared was coated with a 0.3 mm spatula onto release paper and, after curing at 160 DEG C., gave a non-tacky structure with a filled structure in 4 minutes, soft elastic and smooth. suitable for lamination immediately.

Example 5 / Up to 1670 g of polypropylene glycol with mol. 20 g of 1,2-diaminoethane and 20 g of aminoethylethanolamine were added at a weight of 2000, and the mixture was bubbled with carbon dioxide, dried through a 4A0 molecular sieve, while stirring, until the reaction to the amino group was negative. Then, 291 g of toluene diisocyanate, 0.2 g of dibutyltin dilaurate and 2 g of methyl morpholine were added. The mixture was stirred for 60 minutes and then reacted at room temperature for 10 hours.

G of kaolin and 2 g of a color batcher composed of 3 parts by weight of a silicone surfactant and 1 part by weight of a phthalocyanine pigment were mixed into 100 g of the mixture thus prepared. The mixture was painted onto a release paper and a spatula with a 0.3 mm slot. After curing for 4 minutes, 20 ° C formed a non-adhesive, smooth, even elastic and vapor-permeable product.

Claims (1)

SUBJECT OF THE INVENTION ----- · - 1. Alkanolamine carbamate extenders for thermoreactive systems, characterized in that they contain alkanolamines of the aliphatic, cycloaliphatic or aromatic type series - “- O · -O · -οι» HO— / C / Wherein R ₁ , R ₂ are H, CH ₃ , C ₃ H ₃ , C 1 H ₈ , C 4 H ₃ - (CH ₂ ) _y -NH ₂ , - (CH _{2) z} -OH R ₃ is H, CH ₃ , C ₃ H ₃ , -CB ₃ OH R _{4 is} H, CH ₃ ,. 208984 ax is 2-6 2. The extenders according to claim 1, characterized in that they are 2,3 that are a mixture of at least two alkanolamines with an aminoz of 2-4, carbon dioxide blocked groups. their amino groups are blocked by oxide; carbon dioxide.