CS229661B2 - Feeing mixtures containing sensitive substances to oxidation respectivly master composition to produce them - Google Patents

Abstract

Compound feed containing substances sensitive to oxidation, respectively. masterbatches to create them optionally together with another antioxidant such as 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, characterized as being antioxidant the component includes (2,2-dimethyl-1,2-dlhydroquinolin-4-yl) imethylsulphonic acid And / or salts thereof by weight from 0.001 to 10% by total the weight of the mixture. Premixes with antioxidant effect to form of the aforementioned mixtures, characterized by as being an anti-oxidant component (2,2-dimethyl-1,2-dihydroquinolin-4-ylmethylsulfonic acid) and / or her salts in an amount of 0.01 to 10% by weight, based on the total weight premix, together with an inert carrier.

Description

229681

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to feed compositions containing oxidation-sensitive or pre-admixture-sensitive substances, which mixtures or masterbatches are stabilized by the addition of (2,2-dimethyl-1,2-dihydroquinolin-4-yl) methylsulfonic acid and or to go.

(2,2-Dimethyl-1,2-dihydroquinolin-4-yl) methylsulfonic acid (hereinafter referred to as "sulfonic acid") and its salts with distinguishing antioxidant properties and can therefore be used as antioxidants in various mixtures containing oxidation-sensitive substances. These compositions may be a feed mixture or a masterbatch to form, optionally with a fat content.

Feeds used in large numbers of cattle breeds always contain biologically active substances that are susceptible to oxidation. As a rule, these substances stabilize anti-oxidants which, at an effective concentration, must not have a detrimental effect on the living organism and are to be removed quickly from the organism without leaving any residue.

It is known that certain 1,2-dihydroquinoline derivatives possess valuable antioxidant properties. Preferred examples of these compounds are, for example, in Hungarian Patents Nos. 149 496, 157 370, 161 563 and 162 358, in South African Patent Publication No. 712 702 and in Japanese Patents No. 70,48-11. 103.

The disadvantage of commercially available 1,2-dihydroquinoline antioxidants is that they are dark colored, non-homogeneous, viscous or amorphous. Due to their good fat solubility and poor water solubility, these compounds can accumulate in the animal tissues and cause discoloration. The advantageous properties of (2,2-dimethyl-1,2-dihydroquinolin-4-yl) methylsulfonic acid and its salts are that they are low toxicity, have very good antioxidant effect, microcrystalline structure, powder they are well soluble in water and white colored, they are therefore particularly suitable for use in compound feeds, food mixtures and premixes. Accordingly, the present invention provides feed compositions containing oxidation-sensitive substances, or mixtures thereof, optionally together with another antioxidant such as 6-ethoxy-2,2,4-trimethyl-1,2-dihydro-quinoline characterized in that (2,2-dimethyl-1,2-dihydro-quinolin-4-yl) -methylsulphonic acid and / or its salts in the amount of 0.001 to 10% by weight, based on the total amount - the amount by weight of the mixture. The subject matter of the invention includes premixes with an antioxidant effect to form the above-mentioned compositions, characterized in that the antioxidant component includes (2,2-dimethyl-1,2-dihydroquinolin-4-yl) methylsulfonic acid and / or or a salt thereof in an amount of 0.01 to 10% by weight, based on the total weight of the premix, with the inert carrier. Further, the present invention includes a premix containing antioxidants and fat, characterized in that (2,2-dimethyl-1,2-dihydro-quinolin-4-yl) -methylsulfonic acid and / or its weight is present as an antioxidant component. an amount of 0.01 to 2% based on the total amount of the premix together with the lipoids and / or emulsifiers. The invention also relates to the above-described feed compositions or premixes containing oxidation-sensitive substances, characterized in that they comprise, as an antioxidant component, 0.00110% by weight, based on the total weight of the mixture, respectively. premix - (2,2-dimethyl-1,2-dihydroquinolin-4-yl) methylsulfonic acid and / or its salts and 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline in a 1: 1 weight ratio.

An antioxidant is preferably added to the feed by means of additives and / or premixes according to the invention. In this way, the oxidizable substances which are essential for maintaining the biological balance of the feed ((3-carboxy, vitamins AE D, etc.) are already stabilized at an early stage of use. Stabilization is of paramount importance when trace elements catalysed by oxidation.

The feeds can then be stored for a long time without any alteration of readily oxidizable biologically active substances contained in the compositions. The feed additives and additives of the present invention comprise (2,2-dimethyl-1,2-dihydro-quinolin-4-yl) -methylsulfonic acid and / or salts thereof in an amount of from 100 to 100,000 ppm, depending on the field of use. Preferred is a homogeneous mixture of antioxidants and an oxidation-sensitive substance, which mixture is then supplemented with other ingredients of the premix or additive to the feed. The masterbatches contain, for example, dry forage seeds, or various products of the mill industry, as a carrier. Then the premix is mixed with the other ingredients of the feed and converted into feed, ready to feed.

Typical ingredients of the feed are corn cob, soy meal, fisheye, beet sugar, wheat flour, milky meal, sunflower extract. As feed additives, dicalcium phosphate, feed lime, feedstuff, granulated feed can be used. The feed additives may contain various diluents, solvents, lubricants, carriers, and other formulating agents. Using the above ingredients, feed additives can be formulated as powders, granules, powder blends, solutions, emulsions, and the like.

Feed mixtures can be prepared by adding (2,2-dimethyl-1,2-dihydroquinolin-4-yl) methylsulfonic acid and / or its salts as an antioxidant to the feed mixtures

Not only with the premixes containing the oxidation sensitive ingredients, but also as the so-called "antioxidant premix" or "antioxidant fat blend". In this case, the antioxidant is mixed with inert materials or fats, and the resulting antioxidant or fat antioxidant premixes are added to the food or feed compositions. Fat antioxidant compositions. they may optionally also contain emulsifying agents.

The valuable antioxidant properties of (2,2-dimethyl-1,2-dihydroquinol-4-yl) methylsulfonic acid and its salts are exemplified by the data in Table I. These data represent average results of many comparative tests. At four times its usual concentration (about 1000 ppmj, the sodium salt of the sulfonic acid is markedly effective in protecting sunflower oil from rancidity. Sunflower oil has been used as the material in the tests, which has been pre-depleted). Samples were kept at 28 ° C in an uncovered flask with a flask, and the peroxide number was determined by the Wehler method at the intervals indicated in Table I. The results show that the antioxidant activity of the sodium salt (2,2- dimethyl-1,2-dihydropholinolin-4-yl) methylsulfonic acid is greater than the antioxidant activity of the compounds used for comparison. the test, the efficacy of sodium salt of (2,2-dimethyl-1,2-dihydroquinolin-4-yl) -methylsulphonic acid for carotene preservation in the fodder plant was investigated compared to samples containing no antioxidant agent, containing the commercially used antioxidant "BHD".

The change in carotene content of lucerne was monitored under normal conditions at 26 ° C at 70% relative humidity in diffuse light. The results obtained are shown in Table II. It is clear from these results that (2,2-dimethyl-1,2-dihydroquinolin-4-yl] methylsulfonic acid and its sodium salt, respectively, have a strong carotene preservation effect).

(2,2-Dimethyl-1,2-dihydroquinolin-4-yl) -methylsulfonic acid and / or its salts may advantageously be combined with known lipophilic antioxidants, especially when the oxidation susceptible substance is but strongly lipophilic. A preferred combination of (2: 1) sodium salt of (2,2-dimethyl-1,2-dihydroquinolin-4-yl) methylsulfonic acid with the known Ethoxichin (see Table 1).

Further details of the invention will emerge from the examples which follow, which illustrate the invention without limiting its scope. EXAMPLE 1 In a countercurrent, three-stage conventional mixer, this premix premix is prepared: vitamin A 100,000 NE vitamin D 220,000 NO vitamin E 1500 NO vitamin K 250 mg vitamin B1 200 mg vitamin B-600 mg vitamin B -6 200 mg vitamin B-12 2 mg vitamin C 1500 mg Ca-d-pantothenate 1300 mg folic acid 30 mg nicotinic acid 3500 mg biotin 2 mg sodium acid salt (2,2-dimethyl-1,2-dihydroxychinolin-4) -yl) methylsulfonic acid 14,000 mg colin chloride 60,000 mg clopidol (3,5-dichloro-2,6-dimethyl-4-pyridinol 12,500 mg

ZnSOá. H2O at 5200 mg Zn2 +

Ca (JO5) 2. H2O in an amount corresponding to 100 mg of iodine

CaSO4.7 H2O equivalent to 15 mg Ca2 + MnO (amorphous)

in an amount corresponding to 6600 mg of Mn 2+ CuSO 4. 5 H2O at 500 mgCu2 +

FeSOé. 7 H2O in an amount corresponding to 3000 mg Fe2 +

Na2SeO3 in an amount corresponding to 8 mg of Se4 + carrier (wheat flour) to make up to 1000 g. The premix is mixed with 100 kg of feed mixture, optionally together with feed phosphorus and calcium, to obtain a homogeneous mixture. Example 2

In a three-stage, countercurrent, rapid poultry feed mixer, a premixing egg is prepared: for vitamin A 1 000 000 NE vitamin D-3 200 000 NO vitamin E 1600 NE vitamin K 200 mg vitamin B 200 mg vitamin B-2 500 mg vitamin B- 200 mg vitamin B-12 2 mg 229661 r vitamin C 1000 mg

Ca-d-pantothenate 1300 mg folic acid 30 mg nicotinic acid 3000 mg mixture (2: 1) sodium salts of (2,2-dimethyl-1,2-dihydro-quinolin-4-yl) methylsulfonic acid

Ethoxichin 12,000 mg colin chloride 50,000 mg DL-methionine 40,000 mg

ZnSCU. HaO in an amount corresponding to 5200 mg Zn2 + Ca (JO3) 2

in an amount corresponding to 100 mg of iodoCoSO4. 7 H2O equivalent to 15 mg Co2 + MnO (amorphous)

in an amount corresponding to 6600 mgMn 2+ CuSCl 2. 5 HzO

in an amount corresponding to 500 mg of Cu2 + FeSOd.7H2O corresponding to 3000 mg of Fe2 + NaSeO3 equivalent to 8 mg of Se4 + carrier (wheat flour) to be added to 1000 g. Mix the premix with 100 g of the feed mixture, together with the feed if necessary. phosphorous and calcium-containing feeds, thereby obtaining a homogeneous mixture. Example 3

For pig fattening, the following premix is prepared: vitamin A 1,000,000 NE vitamin D-3 140,000 NO vitamin E 1600 NE vitamin K-3 160 mg vitamin B-2 500 mg vitamin B-6 200 mg vitamin B-12 2 mg vitamin C 250 mg Ca-d-pantothenate 1200 mg nicotinic acid 1500 mg (2,2-dimethyl-1,2-dlhydroxychinolin-4-yl) methylsulfonic acid sodium salt 1500 mg colin chloride 40,000 mg zinc bacitration 1500 mg L-lysine hydrochloride 40,000 mg

CoSO4.7 H2O

in an amount corresponding to 3500 mg of Co2 + CuSO2.5 H2O

in an amount corresponding to 5000 mg of Cu2 + FeSo4.7H2O in an amount corresponding to 12 000 mg of Fe2 + carrier (wheat flour) to be replenished to 1000 g. The premix is homogeneously mixed with 100 kg of the feed mixture. Example 4

In the two-stage epicyclic "Nautor" mixer, prepare the following pre-mix for feeding dairy cows:

Vitamin A 350,000 NO

vitamin D-3 300 000 NE (2,2-dimethyl-1,2-dihydroquinolin-4-yl) methylsulfonic acid calcium salt 1000 mg

MgO in an amount corresponding to 150,000 mgMg2 +

ZnSOd. H2O ý equivalent to 14 000 mg Zn2 + Ca (JO3) 2 equivalent to 500 mg of iodine (amorphous)

in an amount corresponding to 9000 mg of Mn2 + CoSO4.7 H2O

in an amount corresponding to 600 mg of Co2 + CuSO4.5 H2O

in an amount corresponding to 2500 mg of Cu2 + FeSO4.7H2O in an amount corresponding to 30,000 mg of Fe2 + carrier (wheat flour) to 1000 g. The premix is homogeneously mixed with 100 kg of feed, optionally together with feed additives containing phosphorus and calcium. Example 5

Using the broiler premix obtained in Example 1, the following broiler feed is prepared: maize meal 56.3% wheat flour 10.0% soybean meal (47 ° / o, extracted) 22.0% fish meal (70%) 8.0%

ZnSCU. H2O in an amount corresponding to 9000 mg Zn2 + Ca (JO3) 2 in an amount corresponding to 100 mg iodine 229661 dicalcium phosphate 1.3 ιθ / ο feed lime 1.0% feed salt 0.4% premix for broilers 1.0% 100.0% Example 6

Using the masterbatch obtained in Example 2, the following feedstock is prepared: corncob meal 54.5% wheat flour 10.0% fish meal (70%) 1.0% soybean meal (47%) 16.5% sunflower extract 3.5% alfalfa meal 5.0% dicalcium phosphate 1.6% granulated feed (forage) 6.5% feed salt 0.4% premix (from example 2) 1.0% 100.0% Example 7 0.5 weight% part of the sodium salt of (2,2-dimethyl-1,2-dihydroquinolin-4-yl) -methylsulphonic acid is mixed with soy lecithin (50%) and then 97 parts by weight of fat and a component are added blends homogeneously. On the basis of the obtained antioxidant mixture, the rat is prepared as described in Example 8. 10 Example 8

Based on the antioxidant / fat mixture obtained in Example 7, the following nutrients are prepared for rat: fish meal (70% crude protein) 13.0% soybean meal (extracted, 47% protein) 34.0% antioxidant / fat mixture Example 7 4.0% Corn Maize Meal 26.0% Bran 8.0% Beet Sugar 10.0% Mineral 3.0% Premix 2.0% 100.0% Example 9 25 g Sodium Acid Salt (2, 2-Dimethyl-1,2-dihydroquinolin-4-yl) methylsulfonic acid is mixed homogeneously with 975 g of limestone flour and the resulting premix is mixed into the feed mixtures in an amount of 1%. EXAMPLE 10 16 g of (2,2-dimethyl-1,2-dihydroquinolin-4-yl) methylsulfonic acid sodium salt are mixed with 9 g of Ethoxichin, adsorbed with 4 g of silica. The pre-mixture obtained is mixed in 0.5% of the feed mixtures.

Table I

Protecting sunflower oil from rancid days

without anti-250 ppmoxidant XAX peroxide number 250 ppm 250 ppm 250 sodium 250 ppm mixtureEthoxi- BHT salt of acid (2: 1) sodium quinoline (2,2-salts (2,2-dimethyl-dimethyl-1,2) -dihydrogen-1,2-dihydro-quinoline-4-quinolin-4-yl-methanesulphin-4-yl) -phosphonic acid with ethoxysulphonamine at 100 ppm of the acid sodium salt (2,2-dimethyl- -1,2-dihydro-quinolin-4-yl) -methylsulphon 1 2 1 1 1 1 1 0 2 12 9 8 8 7 6 2 7 24 20 17 19 15 15 5 12 55 45 39 37 35 33 11 15 90 68 58 55 54 55 16 18 139 96 81 76 72 76 19 XAX = 2-methylene-bis- (2,2,4-trimethyl-1,2-dihydroquinolineEthoxichin = 6-ethoxy-2,2,4-trimethyl- 1,2-dihydroquinolinBHT = 2,6-di-tert-butyl-4-methylphenol

Claims (3)

Table II Change in Carotene Concentration in Lucerne Meal Number of Days without Antioxidant Carotene mg / kg 250 ppm BHT 250 ppm Sodium Salt (2,2-dimethyl-1,2-dihydroquinolin-4-yl) methylsulfone on 1 135 137 138 7 114 124 131 28 80 98 112 49 57 71 92 70 34 46 84 FLOATING SUBSTANCES 1. Feed mixtures containing sensitive substances 3. Pre-mixes according to item 2 containing antioxidants or antioxidants. premixes to their oxidizing component and fat, optionally comprising, together with other antioxidants, an antioxidant component such as 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline characterized in that the antioxidant component comprises (2,2-dimethyl-1,2-dihydroquinolin-4-yl) methylsulfonic acid and / or its salts in a weight ratio of 0.001 to 10%; based on the total mass of the mixture. 2. A premix according to claim 1, wherein the antioxidant component is (2,2-dimethyl-1,2-dihydroquinolin-4-ylmethylsulfonic acid and / or its salts in an amount of 0.01 to 10% by weight). to the total amount of the pre-mixture, together with the inert carrier, sodium (2,2-dimethyl-1,2-dihydroquinolin-4-ylmethylsulphonic acid and / or its salt in an amount of 0.01 to 2% by weight) to the total amount of pre-mixture, together with lipoids and / or emulsifiers. 4. Feed mixtures, respectively. 3. A method according to claim 1, wherein the antioxidant component comprises, in an amount by weight of 0.001 to 10% by weight of the total weight of the mixture, or an acid mixture (2,2-dimethyl-1,2-dihydroquinoline). 4-ylmethylsulfonic acid and / or salts and 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline in a 1: 1 weight ratio.