DEF0012902MA - - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

Registration date: September 28, 1953 Reported on July 19, 1956

GERMAN PATENT OFFICE

The production of high molecular weight, cross-linked plastics by converting isocyanate groups Polyesters with glycols, the at least two optionally condensed aromatic ring systems has already been proposed (patent application F 12 030 IVb / 39b). The execution of this The process can either be carried out in such a way that the polyester containing isocyanate groups with the abovementioned Glycols is reacted, the conversion ratios being chosen so that less glycol is used than corresponds to the free isocyanate groups of the polyester. Another Embodiment consists in using more glycol than the isocyanate groups of the polyester corresponds to, and adding further diisocyanate at a later stage of the reaction. The latter Method allows the reaction to be carried out in separate stages, which is important for processing is essential. As diisocyanates for that process in particular diphenylmethane diisocyanate, p-phenylene diisocyanate and 1,5-naphthylene diisocyanate suitable.

When processing high-molecular, cross-linked plastics, it is important that high-molecular-

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F 12902 IVb / 39b

Cellular, linear products are formed that can be stored for any length of time and only then for higher ones Temperatures or by adding a component to the crosslinked ■ "state. Only below These. requirements is a processing of a

^: Plastic ¹ in'der <for rubber or butadiene polymers known manner possible.

According to the invention it was recognized that this requirement is met to an excellent extent if

ίο one linear or predominantly linear polyester and Glycols which contain at least two, optionally condensed, aromatic ring systems with such Diisocyanates that contain two isocyanate groups that react in a kinetically non-uniform manner in the molecule, reacts in such a "* quantity ratio, that after the reaction has ended, free hydroxyl groups are still present. In a later At this point, the further reaction with diisocyanates, the kinetically uniform isocyanate groups, can then take place contain.

The polyesters preferably applied as the starting material for the present invention are most conveniently made from essentially saturated aliphatic products.

The following acids are mentioned here: malonic acid, succinic acid, Adipic acid, methyladipic acid, maleic acid, carbonic acid, dihydromuconic acid, thiodipropionic acid, Diethyl ether dicarboxylic acid, sebacic acid, suberic acid and higher dicarboxylic acids. As glycols are listed: ethylene glycol, 1,2-propylene glycol, i, 3-propylene glycol, i, 3-butylene glycol, i, 4-butylene glycol, I, 6-hexanediol, methylhexanediol-i, 3, 1, 4-butenediol, Diethylene glycol, thiodiglycol, 2,2'-dimethyli, 3-propylene glycol. Oxycarboxylic acids can also be used in the manufacture of polyesters, provided, however, that there is a tendency towards Polycondensation is stronger than that for ring formation and that sufficient quantities of glycol are present, to ensure the formation of hydroxyl end groups. In addition, mixtures of different acids and glycols can be used, whereby one mixed polyester. Instead of acids and, Glycols, other bifunctional reactants can also be used in smaller amounts. When Examples include compounds that contain aromatic nuclei, such as phthalic acid. Or 'terephthalic acid, aromatic or aliphatic diamines, such as. B. phenylenediamines, naphthylenediamines, piperazine, Ethylenediamine, as well as amino alcohols, such as. B.

Aminopropanol or oxethylaniline. The polycondensation of the components takes place in known manner by heating at ibo to 250 ⁰ instead. By using a small excess of glycol and heating for a sufficient length of time, it is ensured that the polyester has practically no acid number. The OH number should be between 20 and 80, preferably between 40 and 60 .: This corresponds to a percentage of 0.6 to 2.4, preferably 1.2 to 1.8% of free hydroxyl residues. Before the reaction with the diisocyanates takes place, the polyesters produced in this way must be freed of any moisture that may adhere to them. This ■ is done by heating to 100 to 150 ° in vacuo or by passing inert gases through at the same temperature,] '. "Among the acids, adipic acid is preferred and, among the glycols, ethylene glycol and 1,2-propylene glycol. ..

This gives linear products which are perfectly soluble in solvents such as glycol / monomethyl ether acetate and which can be processed perfectly on the roller even without the addition of auxiliaries or roller-repellent agents. This results in completely smooth pelts that can be stored for any length of time without being crosslinked. These linear storable products can then be reacted at a selected point in time with an excess over the amount of an aromatic diisocyanate calculated on the still existing hydroxyl groups, which contains two kinetically "practically uniformly reacting isocyanate groups in the molecule roller takes place, occurs at moderately elevated: temperature still no change of the thermoplastic material and a soluble only in the deformation in the heat performance of the c Vernetzungsyorgang to form a 'high-grade elastic material...

The first phase of the reaction can be carried out by two different methods. On the one hand can taking into account the quantitative ratios given above, c as mixture of linear polyesters and of the glycol with the diisocyanate, which is kinetic. unevenly reacting isocyanate groups contains, react. On the other hand, the glycol in question can also be used after the reaction has ended may be added between the polyester and the diisocyanate.

Diisocyanates with kinetically unevenly reacting isocyanate groups are aromatic diisocyanates in the o-position to an isocyanate group has a substituent such. B. an alkyl, aryl radical, or halogen, or those diisocyanates which have both an aromatic and an aliphatic in the molecule or hydroaromatically bound isocyanate group (see Ang. Chem., A 59, pp. 263 and 264 [1947]). Such diisocyanates are z. B. named:

1, 2, 4-tolylene diisocyanate, 3-nitro-4, 4'-diphenyl diisocyanate, Hexahydrobenzidine diisocyanate and i-chlorine

2,4-phenylene diisocyanate. Of course, these can also be mixed with small amounts of diisocyanates be used with uniformly reacting isocyanate groups.

Glycols which contain at least two optionally aromatically condensed ring systems are especially the 1,5-naphthylene-ß-dioxätb.yläther.

0-CH ₉ -CH ₉ -OH

HO-CH ₂ -CH ₂ -O,

mentioned. Furthermore, the / 3-Dioxäthyläther des 4,4'-Dioxydiphenyl-i, called i'-cyclohexane. Also this',

950/504

F 12902 IVb / 39b

If necessary, small amounts of simple glycols can be added to the compounds.

Among the diisocyanates with isocyanate groups that react kinetically uniformly, diphenylmethane diisocyanate is said to be the main one as well as p-phenylene diisocyanate, i, 5-naphthylene diisocyanate, benzidine diisocyanate called.

The linear polyesters, which are preferably suitable as starting materials for the process,

ίο are made from essentially saturated, aliphatic Components manufactured. The acids are adipic acid, succinic acid, sebacic acid, thiodipropionic acid, Ethylene glycol, butylene glycol, i, 2-propylene glycol, etc. are named as glycols. As glycols can also other bifunctional reactants and the compounds used according to the invention with two aliphatically bonded hydroxyl groups and aromatic ring systems condensed in small amounts will.

example 1

500 parts of an adipic acid ethylene glycol poly

Esters with the OH number 56 and the acid number 1 are mixed with 74 parts of 1.5 ~ naphthylene - /? - dioxäthylether and heated ^{to 150 0 in a vacuum at 20 mm.}

After 15 minutes, the mixture is cooled to 115 °, with a larger part of the "bulky" glycol

■ crystallizes. 87 parts of 1,2,4-tolylene diisocyanate are now added. The temperature rises to about 140 ⁰ , and the separated glycol goes completely into solution.

After cooling to 125 ⁰ is cast in the block and subsequently heated for 20 hours at ioo °. The linear elongated polyester thus obtained, which is mono- in glycol. methyl ether acetate is soluble, is then rolled out on the roller to form a smooth skin.

The further processing of the storable process products can be carried out as follows:

A. For the preparation of the crosslinked highly elastic resin are rolled on 100 parts of the ex- tended polyester 1.9 parts of diphenylmethane diisocyanate on the roller and then pressed at 140 ^0th The non-tabletted diisocyanate containing extended polyester can be at 50 to 70 ⁰ to hoses, spray tire protectors and so on. -

Mechanical values of the pressed panels:

Strength . 0.4 cm

Tear strength 310.0 kg / cm ²

Elongation at break 720.0%

Load at 300% elongation 78.0 kg / cm ²

Ring structure 35.0 kg abs.

Elasticity 45.0

Tear strength fan test .. 40.0 kg / cm

Pin pull-out strength 68.0 kg / cm

B. If on 100 parts extended polyester 3.8 parts Diphenylmethandiisocya'.iat rolled, is obtained during the pressing at 140 ⁰ an elastic plastic having the following mechanical properties:

Thickness 0.33 cm

Tear strength 320.00 kg / cm ²

Elongation at break 720.00%

Load at 300% elongation 87.00 kg / cm ²

Ring structure 31.00 kg abs.

(calculated on 0.4 cm 37.50 kg abs.)

Elasticity 45, oo

Tear strength fan test .. 40.00 kg / cm
Pin pull-out strength 70.00 kg / cm

The mechanical values were determined after storage for 20 hours at 100 °.

Example 2

Parts of an adipic acid-ethylene glycol polyester with the OH number 56 and acid number 1 are dehydrated with parts 1, s-naphthylene-ß-dioxäthylether, as described in Example 1, and then successively with 87 parts 1,2,4- Tolylene diisocyanate and 1.5 parts of 1,4-butylene glycol were added. After raising the temperature to 140 ° and cooling to 125 ⁰ is cast in the block and subsequently heated for 20 hours at ioo °. A skin made therefrom on the roller was z. B. with 3.8 parts of diphenylmethane diisocyanate, based on 100 g of extended polyester, rolled and pressed for 30 minutes. After storage for 2 hours at 100 °, the mechanical values correspond to those of Example 1.

Claims (3)

Patent claims: 1. Process for the production of storable molded articles with diisocyanates to give rubber-elastic molded articles Processable plastics made from polyesters, glycols and diisocyanates, characterized in that mixtures of linear or predominantly linear polyesters and glycols containing at least two, optionally condensed, contain aromatic ring systems, with diisocyanates, which react kinetically non-uniformly Contain isocyanate groups in the molecule, in one to implement the free hydroxyl groups Inadequate amounts of compounds contained in the mixture are converted. 2. The method according to claim 1, characterized in that that still small amounts of a ring-free or at most one ring-containing glycol can be used with. 3. Further development of the method according to claim 1 and 2, characterized in that the glycol, which contains at least two, optionally condensed, aromatic ring systems, kinetically unevenly only after the reaction between the polyester and the two has ended reactive diisocyanate containing isocyanate groups is added.