HU189252B - Method for producing industrial basic material process able by plastic industrial technologic method from natural materials consist of keratine - Google Patents

Abstract

Keratin contg. natural substances are partially hydrolysed to liberate amino amino gps. to the skeleton of the keratin molecule without breaking skeletal bonds, and the hydrolysis is discontinued. The resulting intermediary prod. is reacted with an aliphatic or heterocyclic aldehyde having 1-6 carbons. The reaction prod. is opt. comminuted.

Description

The present invention relates to a process for the production of an industrial raw material. The process of the present invention provides an industrial starting material from keratin-containing natural materials which can be processed into a desired solid product by plastic technology and which retains the favorable skeletal structure of the natural material even after chemical treatment to obtain favorable ductility. If, for example, the process of the present invention provides a heat-curable, extrudable, bakable base material from a chicken pen, and a feather body is detected in the product, which increases the strength of the product material. /

It is known that so far the utilization of keratin-containing materials in the plastics industry is relatively low. The known use of keratin-containing materials is to hydrolyze the keratin chain and then react the hydrolyzed protein with one of a variety of organic compounds to form a synthetic fiber from the reaction product. Natura, 203, 484 (1964)]. The chemical basis for this is that hydrolysis liberates amino groups which can be reacted in a manner known per se. Plastic film is also made of keratin-containing material in a similar way. J. Appl. Pol. Sci. (25/5 (1980), 738-794), which is also referred to in Chemical Abstracts [93, 8840], describes a process for grafting a wool-derived protein with acrylonitrile and a grafting product from fractional precipitation. they make a movie.

A common feature of the processes known hitherto for the commercial use of keratin-containing materials is that the macromolecules bearing the functional groups formed on the starting material are dissolved in the reaction mixture as an industrial starting material, such that the favorable mechanical properties of the structural backbone of the starting material can no longer be transferred to the reaction product.

The present invention is based on the discovery that when hydrolysis is applied only partially, namely when the solid backbone of the starting material is present (e.g., the feather backbone for the chicken pen starting material), but the amino acid groups are already liberated on the solid backbone. reacting the intermediate thus obtained with an aliphatic and / or heterocyclic aldehyde to obtain a product which can be converted into a solid body of the desired shape by plastics processes; if e.g. the resulting product has a thermosetting property, can be extruded, extruded, etc. in suitable shapes such that the skeletal structure retained during partial hydrolysis is incorporated into the thermosetting target product, thereby significantly increasing its strength.

The present invention enables the versatile use of keratinous materials and thus many of the keratinous materials which have been hitherto wasted as waste can be utilized in the industry.

In general, the use of lower aldehydes is preferable, it may be preferable to use a higher chain reagent, especially in the case of heterocyclic aldehyde, so it is generally stated that the partially hydrolyzed crude product is reacted with C 1-6 aldehyde; our experiments e.g.

the use of furfural has been shown to be beneficial.

The thermosetting product obtained by the process of the invention can be shown to behave similarly to known types of thermosetting materials, e.g. the aminoplasts. 11a, it is subjected to heat and / or compression in the shape of the desired target product, the medium is cured, solidified within a short period of time and takes the shape in which the heat and / or compression effect is obtained.

It may be convenient to crush the reaction product, e.g. 0.5 to 3 mm in particle size in order to make the material

- be homogeneous and

- the number of functional groups on the keratin backbone relative to the surface is sufficient to provide a thermosetting process.

Our experiments have confirmed the surprising result that the partially hydrolyzed, predominantly intact peptide-linked keratinous materials react with aldehydes to the extent that they produce a product which can be used as a thermosetting industrial raw material, which melts and then hardens under heat and / or pressure.

In a preferred embodiment, the starting material is a strong alkali, e.g. is hydrolyzed in aqueous solution of sodium hydroxide 1G20, preferably 3-8%, at 0-100, preferably 30-70 ° C for 2-200 minutes, preferably 10-40 minutes, the resulting suspension is neutralized and then washed and / or filtered and The intermediate thus obtained is reacted with the aldehyde.

The aldehyde may be used with or without a solvent, preferably in an amount of 0.04 to 4, preferably 0.4 to 1 mol, per 100 g of the starting material. The reaction time is generally 30 to 600 minutes, preferably 120 to 300 minutes, and the reaction temperature is usually 0 to 200 ° C. The reaction product is filtered off and dried, usually at a temperature between 20 and 200 ° C. The condensation in the vapor phase is suitably carried out at a temperature of 60-180, preferably 90-100 ° C, and a pressure of 30-500, preferably 80-250 Pa.

The present invention provides valuable industrial raw materials from mostly difficult-to-use, often wasted keratin materials by simple technology and good yields, while rescuing the structure of the starting material strength into the raw material and even into the target product.

/. Example 1 A chicken pen and 150 ml of water are shaken in a 500 ml flask until the pen is wet, losing its water repellent properties, which require approx. Shaking for 5 minutes is sufficient. An aqueous solution (150 ml) containing 4% sodium hydroxide was added and the mixture was placed in a water bath at 60 ° C and stirred slowly for 35 minutes. The material then loses its feathers, but the fibrous structure is retained. The reaction mixture was neutralized to pH 7-7.5 with hydrochloric acid, and the fiber retained was filtered and washed twice with 300-300.

189.252 ml of water and filtered again. The still wet material is returned to the flask, 150 ml of a 37% formalin solution is added and the mixture is refluxed gently for 5 hours.

In a press machine, pressed at a temperature of 140 ° C, a probe is pressed from the air-dry product at a pressure of 150 bar. The fibrous design on the section of the wand is clearly recognizable. The strain-bending strength of the dipstick is 23 cm.kp / cm ² .

Figure 1 shows the natural starting pen used for the experiment. Figure 2 shows the deformation of the pen upon interruption of partial hydrolysis. Figure 3 is a sectional view of a 0.2 mm thick die film.

The figures are approx. they were made three times magnified.

Figure 2 shows that the skeletal structure of the pen did not disintegrate during partial hydrolysis despite the disappearance of the thinnest fibers and dissolution of some of the protein content. It can also be seen in Figure 3 that the fibrous backbone structure has also been transferred to the final product, the dipstick.

counterexample

Example 1 was repeated except that the alkaline hydrolysis was continued for 1 hour. Most of the pen material is in solution. The residue was taken up in the same manner as in Example 1 to give a small amount of solid; this material easily melts in the die but has very poor mechanical strength.

Example 2

The procedure of Example 1 was followed except that it was hydrolyzed with 150 ml of 10% sulfuric acid solution at 70 ° C for 5 hours instead of sodium hydroxide solution and neutralized with calcium (II) hydroxide. The impact rod bending strength is 22 cm.kp / cm ² .

Example 3

The procedure of Example 1 was followed, except that the fibrous material was disintegrated with a knife shredder prior to compression so as to consist of at least 80% of particles having a size of 0.5 to 2 mm. An additive (zinc stearate, dye) commonly used in the pressing of aminoplasts is also added. The pressed probe has a homogeneous surface with an impact-bending strength of 26 cm.kp / cm ² .

counterexample

The procedure of Example 3 was followed except that much smaller particles were produced, after which at least 90% of the particles had a particle size of 0.05-0.4 mm. Such breaking of the skeletal structure retained in the intermediate before shredding significantly reduces the strength of the material: the impact-bending strength of the extruded probe is only 13 cm.kp / cm ² .

EXAMPLE 4 A pen is placed in a 100 ml cylindrical pressure vessel with a removable lid. 2 g of ammonia were condensed into it and the temperature was raised to 120 ° C over 2 hours by operating a blow-off valve or a control valve to ensure that the pressure did not exceed 20 Pa. The pressure was then reduced to atmospheric pressure and the vessel cooled to room temperature, then condensed with 2 g of formaldehyde and after the vessel was sealed, the temperature was adjusted to 90 psi over 1 hour. If the pressure does not reach this value, we increase it to the required value with nitrogen pressure. After removal, loose, felt-like solidified material, which is elastic and mechanically solid, can be pushed out when removing the lid of the container.

Example 5

The procedure of Example 1 was followed except that the partially hydrolyzed keratin was replaced with formaldehyde (200 g) at 110 ° C for 8 hours, after which the product was washed twice and dried at 40 ° C under reduced pressure. The test probe made of this product is black and has a shock-bending strength of 31 cm.kp/cm ² .

EXAMPLE 6 Ground bovine horn (g) was mixed with 300 ml of 2% aqueous sodium hydroxide solution in a 500 ml glass flask at 70 ° C for 30 minutes and then neutralized with hydrochloric acid. After filtration, 200 ml of a 40% aqueous formaldehyde solution are added and the mixture is refluxed for 8 hours. After washing and filtration, the coarse powder is dried at 40 ° C under reduced pressure. The impact rod made of this material has a bending strength of 24 cm.kg / cm ² .

Example 7

The procedure of Example 1 was followed except that the pen was treated with water vapor at 6 Pa for 3.5 hours instead of alkaline hydrolysis. The result is the same as in Example 1.

Claims (4)

Claims CLAIMS 1. A process for the production of an industrial starting material from keratin-containing natural material which can be processed into plastics-based solid materials to produce the desired shaped solid product by hydrolysis of the naturally occurring keratin-containing starting material, characterized in that the starting material is subjected to partial hydrolysis. when the starting material is solid 189,252 skeletons (e.g., feathers in the case of distant starting material) are still present, but amino groups have already been released on the solid skeleton, and the resulting intermediate is reacted with aliphatic or heterocyclic C 1-6 aldehyde and the reaction product is optionally crushed, 2. The l. The process of claim 1, wherein the aldehyde reagent is condensed in a vapor phase at a temperature of from 60 to 180, preferably from 90 to 100, at a pressure of from 30 to 500, preferably from 80 to 250 Pa. 3. The process according to claim 1 or 2, characterized in that 0.04-4 per 100 g of starting material in its natural state. preferably 0.4-1 moles of the aldehyde ⁵ is used. 4. A process according to any one of claims 1 to 4, characterized in that the target product - at least 90, - is comminuted into fractions of 0.5 to 3 mm.