CS256118B1 - Polymer sorbent for colloidal and sensory stabilization of drinks and method of its production - Google Patents

Description

The invention relates to a polymeric sorbent for the colloidal and sensory stabilization of beverages containing organic components of plant origin causing haze and sediment formation, in particular in beer, wine, spirits and fruit drinks.

One of the basic requirements for beverages is that their optical and sensory stability be sustained, ie from production to consumption. In practice, the stability of the beverage is required to be long enough and not impaired for the time required for transport, storage, storage, etc. For example, beer produced by conventional technology loses after a certain period of time, ie after 1 to 6 weeks depending on the type. appearance by the occurrence of haze caused by the excretion of colloidal substances. The turbid beer is unusable.

When the stability of a beverage is violated, it is usually not only a change in the appearance of the beverage, but often a deterioration of its sensory properties. The consumer usually evaluates the beverage before use according to its appearance. Therefore, the optical purity of the beverage is considered to be one of its important properties.

Many drinks, such as beer, wine, some spirits and fruit drinks, contain, to a lesser or greater extent, depending on the type and method of production, a certain amount of colloidal substances such as polyphenols, polysaccharides, polypeptides and the like extracts of plant substances such as malt, hops, herbs, etc. These substances are subject to a series of reactions via functional groups such as carboxylic, hydroxyl, etc., after release by extraction from the original plant structure, especially in a freshly prepared beverage to form high molecular components. beverages become insoluble. Thus, the initially soluble organic ingredients in beverages become insoluble and this process results in the elimination of turbidity or sediment, the formation of which is accelerated by the presence of oxygen, some metal ions, temperature, light, mechanical movement and other influences to which the beverage is usually exposed.

In practice, it is very difficult to ensure that the finished beverage is maintained or maintained in such conditions that the reactions would not take place, in particular during transport of storage and sale. The main drawback of beverages containing organic extracts is the formation of colloid hazes or even sediments from their production to consumption. Delaying turbidity in these types of beverages or completely eliminating the causes of their formation is, from a practical point of view, a major problem that needs to be addressed so as not to provide special external conditions in which the beverage is maintained from production to consumption. In order to solve this problem, it is furthermore required that all the characteristics of the beverage be maintained.

Turbidity is currently eliminated in some species by removing from the beverage a substance or substances that cause turbidity without compromising the desired characteristics of the beverage, such as color, foam, taste, etc. Removing turbidity from the beverage beverages are carried out by means of sorbents or stabilizers of various kinds.

These stabilizing agents are usually powdery substances, porous structures that do not dissolve in the beverages and only absorb substances that later cause haze and sediment upon contact with the beverage. Sorbed haze-forming substances are soluble in the beverage at the time of finalization of the beverage production and do not carry the desired characteristics and quality. Current beverage stabilizers are of organic or inorganic origin.

The most commonly used inorganic stabilizers of beverages are xero- and hydrogels, bentonites, various types of clays, etc. The disadvantage of inorganic stabilizers of the sorbent type is their low efficiency and consequently it is necessary to work with a larger amount of these agents. These types of stabilizers of colloidal and sensory stability of beverages cannot be regenerated in a simple manner and consequently their waste causes environmental problems.

In addition, some of them, such as bentonites, cause a sensory change in the beverage by giving the beverage an earthy flavor and reducing the foaming of beer.

Much more effective and economically effective anti-colloidal haze stabilizers are polymer-based or copolymer-based sorbents in porous powder or gel form, such as cross-linked polyvinylpyrrolidone. Some types of polymeric sorbents, especially based on polyamides or modified polyamides as starting materials, are very effective stabilizers of the colloidal and sensory properties of beverages. Their production is carried out in three operations. Firstly, it is the production and isolation of polymers, from which, in a second operation, a composite is prepared by dissolving the polymers at a temperature of 190 to 210 ° C in a melt of a solvent having a melting point of 50 to 100 ° C. In a third operation, the melt solvent is extracted from the composite to form a suspension and the separated sorbent is washed and dried. This procedure gives the final product, i.e. the polymer in powdered porous form - a polymeric sorbent. The production of polymeric sorbents according to this three-step process is economically disadvantageous and has an adverse effect on the cost and certain properties of the end product.

These known polymeric sorbents for stabilizing beverages and the process for their preparation are further improved according to the present invention.

The present invention provides a polymeric sorbent for the colloidal and sensory stability of beverages containing organic ingredients of vegetable origin, in particular beer, wine, spirits and fruit beverages, based on copolymers of poly-6-caprolactam and polyethylene oxide. SUMMARY OF THE INVENTION The sorbent comprises 0.6 to 30% by weight of bonded polyethylene oxide structures, the content of the porous structure in the sorbents according to the invention being 1 to 60%, the mean pore diameter up to 60 µm, the pore volume 0.1 to 5 1 ml / go specific surface area from 0.1 to 60 m / g. The copolymer used preferably has a viscosity limit of 0.5 to 2.2. The invention also relates to a process for the preparation of this polymeric sorbent. The essence of the process according to the invention is that the mixture is mixed

6-caprolactam and alpha, omega-diaminopolyethylene oxide having a molecular weight of 600-5000 are polymerized in the presence of a two-component initiator and activator initiator system, after polymerization the polymer is deactivated and the polymerization product dissolved by adding caprolactam in an amount of 1 to 6 parts by weight After cooling the solution, 6-caprolactam is extracted from the solid composite, whereupon the resulting suspension is washed and dried to the final product. It is preferred that the polymerization of the 6-caprolactam-alpha, omega-diaminopolyethylene oxide mixture be initiated by at least one of 6-caprolactam sodium, sodium hydride, sodium bis (2-methoxyethoxy) -dihydrohydride, sodium tetra-6-caprolactam aluminum aluminum and dilactamato N-bis (2-methoxyethoxo) sodium aluminate.

It is further preferred to activate the polymerization of the mixture of 6-caprolactam and alpha, omega-diaminopolyethylene oxide by at least one of the group consisting of N-acyllactams, such as DOC-acetylcaprolact, or isocyanates such as N-phenylocyanate, toluene diisocyanate or substances derived therefrom. phenylcarbamoyl-6-caprolactam; and the cyclic trimmer of N-phenylisocyanate.

By not isolating the polymerization product but converting it into a porous powder form, the product is dissolved in the melt of 6-caprolactam at 190-210 ° C directly in the polymerization apparatus after the polymerization activity has stopped, and after cooling the solution, 6-caprolactam is extracted from the solid composite. , the suspension is filtered and the product is washed and dried. The polymerization time ranges from 15 to 180 minutes at a temperature of 140 to 240 ° C. The polymerization activity is stopped by the addition of acids such as aminocaproic, citric or phosphoric acid in an amount equimolar to the amount of initiator. The amount of molten 6-caprolactam to dissolve the polymer product ranges from 1 to 6 parts by weight, based on the weight of the polymer product. 2 kg of sorbents produced according to the present invention, when contacted with the beverage strengths containing organic extracts, reduces the content of polyphenol substances from 20 to 45% by weight, and anthocyanogens by 30 to 60% depending on the type of beverage. It provides drinks with colloidal and sensory stability for several years.

The textile properties of the polymeric sorbent according to the invention for the sorption of haze-forming substances from beverages are dependent on the conditions for its production, in particular on the type of initiator, alpha molecular weight, omega-diaminopolyethylene oxide, initiator and activator concentration and 6-caprolactam used to dissolve the polymer. the product when processed into a porous powder form.

The method of stabilizing a beverage of the invention comprises contacting the beverage with the polymeric sorbent statically or dynamically, i.e., adding the sorbent to the beverage in a suitable device and mixing and settling the sorbent followed by filtering the beverage and / or passing the beverage through the polymeric stabilizer layer. Advantageously, however, the polymeric sorbent can be applied by an alluvial technique where the required amount of polymeric stabilizer is continuously added to the beverage stream.

The reduction in the polyphenol content of the beverage is governed by the amount of polymeric sorbent, its solubility capacity, which is dependent upon the texture properties of the sorbents and its chemical composition, or the content of polyethylene oxide segments and their molar mass. The amount of polymeric sorbent required to stabilize the beverage depends on the type of beverage and ranges from 5 to 200 g / 100 L of beverage. The contact time of the sorbent with the beverage ranges from 1 to 180 minutes. The polymeric sorbent of the present invention is regenerated with a sodium hydroxide solution at a concentration of 0.05 to 1% by weight, and after washing to a neutral reaction the sorbent is reused. The regeneration process can be practically unlimited.

In keeping with the above-mentioned conditions for the preparation of the polymeric sorbent and its use for colloidal and sensory stabilization of beverages, a considerably more advantageous economic effect, as shown in the following examples, is achieved over the prior art. Unless otherwise stated, all figures are in% by weight.

Example 1

To a mixture consisting of 900 g of 6-caprolactam and 100 g of alpha, omega-diaminopolyethylene oxide of 1,600 molar mass placed in a 4.25-liter stainless steel reactor equipped with heating, stirring, inert gas supply by thermometer and metering device was added 1.43 mol. % bis (2-methoxyethoxy) sodium aluminum hydride (based on β-caprolactam) in the form of a 70¾ solution in toluene. The reaction mixture was gradually heated to 170 ° C at which time 0.57 mol. % N-acetylcaprolactam. After this operation, the temperature of the reaction mixture rose to 230 ° C in 10 to 20 minutes. The polymerization mixture was maintained at 230 ° C for 60 minutes and after increasing the viscosity of the polymerization mixture to a maximum value that no longer increased. The polymerization activity was stopped by addition of 1.43 mol. % aminocaproic acid (equivalent amount to initiator) into the polymer blend with thorough mixing. Then, the melt polymerization product was dissolved with stirring in 2 kg of molten 6-caprolactam heated to 210 ° C. The dissolution process was followed by a decrease in the viscosity of the reaction mixture.

After stabilizing the viscosity of the reaction mixture solution, the solution was discharged from the reactor into a shallow aluminum vessel of such a size that the solution height was 2 to 5 cm. All the operations described were carried out under a protective nitrogen atmosphere. After cooling the solution, the solid composite of the two solid phases was subjected to extraction with water. This process resulted in a suspension of the copolymer in solution, which was filtered, washed with water and dried to a final water content of about two% by weight. The powdered porous sorbent thus produced was a block copolymer of poly-6-caprolactam and polyethylene oxide of the ABA type, wherein A are poly-6-caprolactam structures. The content of bound polyethylene oxide structures (V) was 8.5% by weight. The specific surface area of the sorbent sample was 2.56 m / g, porosity 39.2%, mean pore diameter 20 µm and pore volume

2.7 ml / g. A 2 g sample of the prepared sorbent was contacted with 12% light beer at room temperature for 30 minutes. After separation of the sorbent, the loss of polyphenol substances was 34.01% by weight and the anthocyanogens by 47.79% by weight in pure beer.

Example 2

A mixture of 800 g of 6-caprolactam and 200 g of alpha, omega-diaminopolyethylene oxide having a molar mass of 3200 was polymerized as described in Example 1 using 2.64 mol% sodium tetra-6-caprolactam aluminum aluminum initiator and 0.92 mol. % Of N-acetylcaprolactam as activator and polymerization activity was stopped by addition of 2.64 mol. % of aminocaproic acid (based on caprolactam in the polymerization mixture). The polymer product in the form of a melt was dissolved in 3 kg of molten 6-caprolactam, and after treatment of the solution and the composite of Example 1, a powder copolymer containing 17.5% by weight of a bonded polyethylene oxide structure was obtained. The specific surface area of the sample was 4.05 m / g, the porosity was 42.00%, the mean pore diameter was 16%, and the total pore volume was 2.1 ml / g. 2 g of this sample was used to stabilize 1 L of 12% light beer as described in Example 1. The loss of polyphenol substances compared to the original state was 32.02% and anthocyanogens 43.20%.

Example 3

A mixture consisting of 950 g of 6-caprolactam and 50 g of alpha, omega-diaminopolyethylene oxide having a molecular weight of 2,000 was polymerized as described in Example 1 using 1.33 mol. % initiator sodium salt of 6-caprolactam and 1.3 mol. % N-acetylcaprolactam as activator. The polymerization activity of the mixture was stopped by addition of 1.03 mol. % of citric acid and the polymerization product dissolved in 2.5 kg of molten 6-caprolactam and the solution worked up to the polymeric sorbent as described above. The bound polyethylene oxide structure 2 of this sample was 3.57% by weight. The specific surface area of the sample was 4.25 m / g, the porosity was 36.8%, the mean pore diameter was 35 µm and the pore volume was 3.1 ml / g.

g of this sorbent was mixed into 1 l of white wine at room temperature and after 30 minutes of contact the sorbent was separated and the content of polyphenol substances was determined in the clear wine. It was determined that the loss of polyphenols compared to the original state was 34.07% and anthocyanogens by 37.4%.

Example 4.

A mixture of 850 g of 6-caprolactam and 150 g of alpha, omega-diaminopolyethylene oxide having a molar mass of 1,200 was polymerized as described in Example 1 using 2.91 mol. % dilactamato-bis (2-methoxyethoxo) aluminate initiator and 0.93 mol. % N-acetylcaprolactam as a polymerization activator. The polymerization activity of the mixture was stopped by the addition of 2.92 moles. % of phosphoric acid and the polymer product were dissolved in 2.3 kg of molten 6-caprolactam and the solution was processed to a sorbent as described above. Content of bound polyethylene oxide structures. 2 in the prepared sorbent sample was 12.5%. The specific surface area of the sorbent sample was 3.6 m / g, the porosity was 39.27%, the mean pore diameter was 27 yum, and the pore volume was 2.37 ml / g.

g of this sample was contacted with apple juice for 30 minutes at room temperature. After separation of the polymeric sorbent, the loss of polyphenol substances in the filtrate was determined by 17% and anthocyanogens by 28%.

Example 5

A mixture of 800 g of 6-caprolactam and 200 g of alpha, omega-diaminopolyethylene oxide of 800 molar mass was polymerized as described in Example 1 using 4.64 moles. % sodium tetra-6-caprolactamaluminate initiator with 1.24 mol. % N-acetylcaprolactam as a polymerization activator. The polymer product was dissolved in 2.4 kg of molten 6-caprolactam at 210 ° C and treated to a polymeric sorbent according to the above procedure. The polyethylene oxide content of the prepared sample was 18% by weight. Specific surface area 4.2 m ² / g, porosity 42%, mean pore diameter 22 µm and total pore volume 2.72 ml / g.

g of this sorbent were mixed into 1 liter of spirits containing herbal extracts, and after 30 minutes of contact, the sorbent was separated and the spirits determined a decrease in polyphenol substances by 37.0% and anthocyanogens by 48.7%.

Claims (4)

SUBJECT OF THE INVENTION 1. Polymeric sorbent for the colloidal and sensory stabilization of beverages containing organic ingredients of vegetable origin, in particular beer, wine, spirits and fruit drinks, based on copolymers of poly-6-caprolactam and polyethylene oxide, characterized in that it contains 0.5 to 30% by weight of bound polyethylene oxide structures, wherein the porous structure of the polymeric sorbent is 1 to 60%, the mean pore diameter is 1 to 60 µm, the pore volume is 0.1 to 5.1 ml / g, and 2 has ^a specific surface area of 0.1 to 60 m / g. 2. A process for producing a polymeric sorbent according to claim 1, characterized in that the mixture is 6-caprolactam and alpha, omega-diaminopolyethylene oxide having a molecular weight of 600-5000 are polymerized in the presence of a two-component initiator and activator initiation system, after polymerization the polymer is deactivated and the polymerization product dissolved by adding 1 to 6 parts by weight of caprolactam 6-caprolactam is extracted from the solid composite, after which the resulting suspension is washed and dried to the final product. 3. A process according to claim 2, wherein the polymerization of the mixture of 6-caprolactam and alpha, omega-diaminopolyethylene oxide is initiated by at least one of 6-caprolactam sodium, sodium hydride, sodium bis (-2-methoxyethoxy) -dihydride aluminum hydride. sodium tetra-6-caprolactam aluminum aluminum and sodium dialactamato-bis (2-methoxyethoxo) aluminate. 4. The process of claim 2 wherein the polymerization of the mixture of 6-caprolactam and alpha, omega-diaminopolyethylene oxide activates at least one of the group consisting of N-acyllactams, such as N-acetyl-6-caprolactam, or isocyanates such as N. phenyl isocyanate, toluene diisocyanate or substances derived therefrom, such as N-phenylcarbamoyl-6-caprolactam and the cyclic trimmer of N-phenylisocyanate.