WO2019080009A1 - N,n-二甲基甘氨酸有机酸复合盐及其组合物和应用 - Google Patents

N,n-二甲基甘氨酸有机酸复合盐及其组合物和应用

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Publication number
WO2019080009A1
WO2019080009A1 PCT/CN2017/107673 CN2017107673W WO2019080009A1 WO 2019080009 A1 WO2019080009 A1 WO 2019080009A1 CN 2017107673 W CN2017107673 W CN 2017107673W WO 2019080009 A1 WO2019080009 A1 WO 2019080009A1
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Prior art keywords
dimethylglycine
ion
organic acid
polyvalent metal
metal ion
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PCT/CN2017/107673
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English (en)
French (fr)
Inventor
彭险峰
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广州英赛特生物技术有限公司
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Application filed by 广州英赛特生物技术有限公司 filed Critical 广州英赛特生物技术有限公司
Priority to ES17929999T priority Critical patent/ES2907015T3/es
Priority to CN201780004137.6A priority patent/CN108349871B/zh
Priority to BR112020006571-4A priority patent/BR112020006571B1/pt
Priority to PCT/CN2017/107673 priority patent/WO2019080009A1/zh
Priority to EP17929999.5A priority patent/EP3670493B1/en
Priority to US16/754,758 priority patent/US11666071B2/en
Priority to DK17929999.5T priority patent/DK3670493T3/da
Publication of WO2019080009A1 publication Critical patent/WO2019080009A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
    • C07C229/10—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
    • C07C229/12—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings to carbon atoms of acyclic carbon skeletons
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K20/00—Accessory food factors for animal feeding-stuffs
    • A23K20/10—Organic substances
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K10/00—Animal feeding-stuffs
    • A23K10/30—Animal feeding-stuffs from material of plant origin, e.g. roots, seeds or hay; from material of fungal origin, e.g. mushrooms
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K10/00—Animal feeding-stuffs
    • A23K10/30—Animal feeding-stuffs from material of plant origin, e.g. roots, seeds or hay; from material of fungal origin, e.g. mushrooms
    • A23K10/37—Animal feeding-stuffs from material of plant origin, e.g. roots, seeds or hay; from material of fungal origin, e.g. mushrooms from waste material
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K20/00—Accessory food factors for animal feeding-stuffs
    • A23K20/10—Organic substances
    • A23K20/105—Aliphatic or alicyclic compounds
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K20/00—Accessory food factors for animal feeding-stuffs
    • A23K20/10—Organic substances
    • A23K20/111—Aromatic compounds
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K20/00—Accessory food factors for animal feeding-stuffs
    • A23K20/10—Organic substances
    • A23K20/142—Amino acids; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K20/00—Accessory food factors for animal feeding-stuffs
    • A23K20/10—Organic substances
    • A23K20/142—Amino acids; Derivatives thereof
    • A23K20/147—Polymeric derivatives, e.g. peptides or proteins
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K20/00—Accessory food factors for animal feeding-stuffs
    • A23K20/10—Organic substances
    • A23K20/163—Sugars; Polysaccharides
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K20/00—Accessory food factors for animal feeding-stuffs
    • A23K20/10—Organic substances
    • A23K20/174—Vitamins
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K20/00—Accessory food factors for animal feeding-stuffs
    • A23K20/20—Inorganic substances, e.g. oligoelements
    • A23K20/24—Compounds of alkaline earth metals, e.g. magnesium
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K20/00—Accessory food factors for animal feeding-stuffs
    • A23K20/20—Inorganic substances, e.g. oligoelements
    • A23K20/26—Compounds containing phosphorus
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K20/00—Accessory food factors for animal feeding-stuffs
    • A23K20/20—Inorganic substances, e.g. oligoelements
    • A23K20/28—Silicates, e.g. perlites, zeolites or bentonites
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K20/00—Accessory food factors for animal feeding-stuffs
    • A23K20/20—Inorganic substances, e.g. oligoelements
    • A23K20/30—Oligoelements
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/76—Metal complexes of amino carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/29—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings
    • C07C309/30—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings of six-membered aromatic rings substituted by alkyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
    • C07C53/126—Acids containing more than four carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
    • C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
    • C07C57/13—Dicarboxylic acids
    • C07C57/15—Fumaric acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
    • C07C63/04—Monocyclic monocarboxylic acids
    • C07C63/06—Benzoic acid
    • C07C63/08—Salts thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
    • Y02P60/80—Food processing, e.g. use of renewable energies or variable speed drives in handling, conveying or stacking
    • Y02P60/87—Re-use of by-products of food processing for fodder production

Definitions

  • the invention belongs to the field of animal feed additives, and in particular relates to N,N-dimethylglycine complex acid salts or solvates thereof and compositions comprising the foregoing salts and their use in the preparation of animal feed additives.
  • Dimethylglycine has a molecular formula of (CH 3 ) 2 NCH 2 COOH. It has white crystal appearance, is soluble in water and ethanol, and is physiologically active in food, cereal beans and liver. Nutrients, natural substances in the metabolic pathways of plants and animals. As a nutritional antioxidant additive, dimethylglycine also shows important physiological and biochemical functions in human and animal health. A large number of animal experiments have found that dimethylglycolic acid is a very safe food-based nutritional supplement.
  • N,N-dimethylglycine is a highly hygroscopic solid that is inconvenient to store and use.
  • the commonly used N,N-dimethylglycine hydrochloride, sodium N,N-dimethylglycine, and potassium N,N-dimethylglycine are also very strong in moisture absorption, and are easy to absorb moisture and deliquescent during storage.
  • the requirements for production equipment and plant facilities are high. Otherwise, the products will be agglomerated due to moisture absorption during the production process, which will not meet the application requirements of the feed processing industry.
  • packaging containing DMG or DMG hydrochloride or alkali metal salt must be tightly sealed. Once the sealing is insufficient, the product will be mildewed due to moisture absorption during storage.
  • the present invention provides a N,N-dimethylglycine salt which is not easily hygroscopic, and the N,N-dimethylglycine salt is an N,N-dimethylglycine organic acid polyvalent metal.
  • the ion complex salt or a solvate thereof has an effect of improving the growth performance of an animal equivalent to or superior to sodium N,N-dimethylglycine.
  • the present invention also provides a feed composition comprising the N,N-dimethylglycine organic acid polyvalent metal ion complex salt or a solvate thereof, and the N,N-dimethyl
  • a feed composition comprising the N,N-dimethylglycine organic acid polyvalent metal ion complex salt or a solvate thereof, and the N,N-dimethyl
  • the present invention provides a multivalent metal ion comprising an N,N-dimethylglycine ion, an equimolar amount with the N,N-dimethylglycine ion, and the N,N- A N,N-dimethylglycine organic acid polyvalent metal ion complex salt or a solvate thereof, which is a chemically equivalent feed acceptable organic acid ion such as a dimethylglycine ion and a polyvalent metal ion.
  • the equimolar amount of the polyvalent metal ion with the N,N-dimethylglycine ion is a divalent metal ion or a trivalent metal ion.
  • the divalent metal ion is an alkaline earth metal ion, which may be selected from the group consisting of Ca(II), Mg(II), and Ba(II). Or Sr(II).
  • the divalent metal ion is a transition metal divalent ion, which may be selected from the group consisting of Cu(II), Zn(II), Fe(II), Mn(II), Cr(II), Cd ( II), Co(II) or Ni(II).
  • the trivalent metal ion can be selected from the group consisting of Al(III), Cr(III), or Fe(III).
  • the organic acid corresponding to the organic acid ion is a polybasic organic acid, and may be selected from the group consisting of fumaric acid, maleic acid, tartaric acid, succinic acid, fumaric acid, malonic acid, malic acid, and dihydroxypropionic acid. , pyruvic acid, glycolic acid, glucuronic acid, galacturonic acid, aspartic acid, glutamic acid, citric acid or oxalic acid.
  • the organic acid corresponding to the organic acid ion is preferably fumaric acid.
  • the organic acid corresponding to the organic acid ion is a linear aliphatic monobasic acid, and may be selected from a C 4 -C 18 linear fatty monobasic acid.
  • the organic acid corresponding to the organic acid ion is an aromatic organic acid, which may be selected from the group consisting of benzoic acid, p-toluic acid, p-chlorobenzoic acid, p-bromobenzoic acid, p-aminobenzoic acid, mandelic acid, and cinnamon. Acid, benzenesulfonic acid, p-toluenesulfonic acid, naphthoic acid, salicylic acid or acetylsalicylic acid.
  • the organic acid corresponding to the organic acid ion is preferably benzoic acid or p-toluic acid.
  • the N,N-dimethylglycine organic acid polyvalent metal ion complex salt comprises N,N-dimethylglycine ion, and the N,N-dimethylglycine ion
  • the N,N-dimethylglycine organic acid polyvalent metal ion complex salt comprises N,N-dimethylglycine ion, and the N,N-dimethylglycine ion
  • the N,N-dimethylglycine organic acid polyvalent metal ion complex salt comprises N,N-dimethylglycine ion, and the N,N-dimethylglycine ion
  • the N,N-dimethylglycine organic acid polyvalent metal ion complex salt comprises N,N-dimethylglycine ion, and the N,N-dimethylglycine ion An equal molar amount of Cu(II) and a chemical equivalent of fumarate ions such as the N,N-dimethylglycine ion and the Cu(II).
  • the N,N-dimethylglycine organic acid polyvalent metal ion complex salt comprises N,N-dimethylglycine ion, and the N,N-dimethylglycine ion
  • the N,N-dimethylglycine organic acid polyvalent metal ion complex salt comprises N,N-dimethyl a base glycine ion, an equivalent molar amount of Zn(II) with the N,N-dimethylglycine ion, and a chemical equivalent of the N,N-dimethylglycine ion and the Zn(II) Fumarate ion.
  • the present invention provides a forage composition comprising at least one of a N,N-dimethylglycine organic acid polyvalent metal ion complex salt or a solvate thereof provided by the present invention. And feedable excipients.
  • the feedable adjuvant is a feedable carrier, a diluent, an excipient, a solvent, or a combination thereof.
  • the forage composition further comprises a feedstock material and or an additional animal feed additive.
  • the additional animal feed additive is a nutritive feed additive, a general feed additive or a pharmaceutical feed additive.
  • the present invention provides the use of the N,N-dimethylglycine organic acid polyvalent metal ion complex salt or a solvate thereof.
  • the N,N-dimethylglycine organic acid polyvalent metal ion complex salt is used in the preparation of an animal feed additive.
  • the N,N-dimethylglycine organic acid polyvalent metal ion complex salt is used in the preparation of an animal feed.
  • the animal is a farm animal selected from the group consisting of livestock, poultry, aquaculture animals or pets.
  • the present invention provides the use of a feed composition comprising a N,N-dimethylglycine organic acid polyvalent metal ion complex salt or a solvate thereof.
  • the use of the forage composition in the preparation of an animal feed additive in some embodiments, the use of the forage composition in the preparation of an animal feed additive.
  • the use of the feed composition in the preparation of an animal feed in some embodiments, uses of the feed composition in the preparation of an animal feed.
  • the animal is a farm animal selected from the group consisting of livestock, poultry, aquaculture animals or pets.
  • the invention also provides a method of improving the performance of a farmed animal.
  • the method comprises administering to the farmed animal a N,N-dimethylglycine organic acid polyvalent metal ion complex salt or a solvate thereof provided in association with the feed.
  • the method comprises administering to a cultured animal a feed composition comprising a N,N-dimethylglycine organic acid polyvalent metal ion complex salt or a solvate thereof provided by the present invention provided by the present invention.
  • the present invention also provides a method for preparing, separating and purifying the N,N-dimethylglycine organic acid polyvalent metal ion composite salt.
  • the N,N-dimethylglycine organic acid polyvalent metal ion composite salt provided by the invention is a salt of N, N-dimethylglycine and an organic acid simultaneously with a polyvalent metal ion, which can reduce N, N-di The moisture absorption of methyl glycine.
  • N,N-dimethylglycine organic acid polyvalent metal ion complex salt or a solvate thereof is used in the preparation of an animal feed additive or feed.
  • Moisture-reducing production equipment for feed or feed additives has reduced requirements for moisture-proof functions and can reduce production costs.
  • the moisture absorption of the product reduces the sealing requirements of the product packaging, and the cost is reduced, and the risk of short-term moisture deterioration of the product due to the damage of the packaging due to accidents during transportation or storage can be avoided.
  • the N,N-dimethylglycine organic acid polyvalent metal ion composite salt provided by the invention has the effect of improving the production performance of poultry and livestock in the breeding experiment, and is equivalent to the N,N-dimethylglycine sodium salt, and some salts even Shows a slightly better improvement.
  • any of the embodiments of any of the aspects of the invention may be combined with other embodiments as long as no contradiction occurs between them.
  • any of the technical features may be applied to the technical features in other embodiments as long as there is no contradiction between them.
  • the present invention provides a polyvalent metal ion comprising an N,N-dimethylglycine ion, an equimolar amount with the N,N-dimethylglycine ion, and the N,N-dimethyl group
  • a polyvalent metal ion comprising an N,N-dimethylglycine ion, an equimolar amount with the N,N-dimethylglycine ion, and the N,N-dimethyl group
  • the "polyvalent metal ion" referred to in the present invention means a metal ion having a +2 valence or a +3 valence.
  • the "equimolar amount" referred to in the present invention is such that the number of polyvalent metal ions is equal to the number of N,N-dimethylglycine ions.
  • isochemical equivalent means that the total anion of the organic acid ion ion is such that the chemical body containing the same molar amount of the N,N-dimethylglycine ion and the polyvalent metal ion exhibits a positive and negative charge balance. status.
  • feed acceptable organic acid ion means that the substance must be chemically or toxicologically related to the constituent feed or edible cultured animal, and the organic acid ion which is not toxic to the animal.
  • the “complex salt” referred to in the present invention means a salt composed of an N,N-dimethylglycine ion and another organic acid ion as an anionic ligand and a metal ion.
  • N,N-dimethylglycine organic acid polyvalent metal ion composite salt is as follows:
  • N,N-dimethylglycine hydrochloride (referred to as DMG hydrochloride) in a lower alcohol organic solvent with an equivalent chemical equivalent
  • DMG hydrochloride N,N-dimethylglycine hydrochloride
  • Neutralization reaction of inorganic base gives free N,N-dimethylglycine, which is mixed with another organic acid at room temperature to obtain a reaction liquid which is further mixed with basic polyvalent metal hydroxide or under alkaline conditions.
  • the valence metal halide reacts to form a corresponding N,N-dimethylglycine organic acid polyvalent metal ion complex salt, and the "equal chemical equivalent" means that the amount of the inorganic base can be used to free DMG hydrochloride to obtain DMG.
  • the lower alcohol organic solvent is methanol, ethanol, n-propanol, isopropanol or n-butanol.
  • the inorganic base is ammonia or an alkali metal hydroxide, carbonate or bicarbonate, including but not limited to sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate. And potassium bicarbonate.
  • another organic acid that is homogeneously mixed with the free form DMG can be selected from the group consisting of polybasic organic acids, linear fatty monoacids, or aromatic organic acids.
  • the polybasic organic acid may be selected from the group consisting of fumaric acid, maleic acid, tartaric acid, succinic acid, fumaric acid, malonic acid, malic acid, dihydroxypropionic acid, pyruvic acid, glycolic acid, glucuronic acid, galacturonic acid.
  • Aspartic acid, glutamic acid, citric acid or oxalic acid is preferably fumaric acid.
  • the linear fatty monobasic acid may be selected from a C 4 - C 18 linear fatty monobasic acid, preferably tetradecanoic acid.
  • the "C 4 -C 18 linear fat monobasic acid” according to the present invention is a non-branched fat monobasic acid having 4 to 18 carbon atoms.
  • the aromatic organic acid may be selected from the group consisting of benzoic acid, p-toluic acid, p-chlorobenzoic acid, p-bromobenzoic acid, p-aminobenzoic acid, mandelic acid, cinnamic acid, benzenesulfonic acid, p-toluenesulfonic acid, naphthoic acid, water.
  • Salicylic acid or acetylsalicylic acid is preferably benzoic acid, p-toluic acid or p-toluenesulfonic acid.
  • the basic polyvalent metal hydroxide reacted with the reaction solution in which the free form of DMG and the organic acid are uniformly mixed may be selected from basic divalent metal hydroxides or basic trivalent metal hydroxides.
  • the basic divalent metal hydroxide is an alkaline earth metal hydroxide.
  • the alkaline earth metal hydroxide is calcium hydroxide (Ca(OH) 2 ), magnesium hydroxide (Mg(OH) 2 ), barium hydroxide (Ba(OH) 2 ) or barium hydroxide (Sr) (OH) 2 ),
  • the corresponding product N, N-dimethylglycine organic acid polyvalent metal ion composite salt comprises a metal ion which is a divalent alkaline earth metal ion, which may be selected from Ca(II), Mg(II), Ba(II) or Sr(II).
  • the basic divalent metal hydroxide is a basic transition metal hydroxide.
  • the basic transition metal hydroxide is copper hydroxide (Cu(OH) 2 ), zinc hydroxide (Zn(OH) 2 ), ferrous hydroxide (Fe(OH) 2 ), and hydroxide.
  • the metal ion contained is a transition metal divalent ion and may be selected from Cu(II), Zn(II), Fe(II), Cd(II), Co(II) or Ni(II).
  • the basic polyvalent metal hydroxide reacted with the reaction solution in which the free form of DMG and the organic acid are uniformly mixed is a basic trivalent metal hydroxide
  • said basic trivalent metal hydroxide The material is preferably iron hydroxide (Fe(OH) 3 ), chromium hydroxide (Cr(OH) 3 ) or aluminum hydroxide (Al(OH) 3 ), and the corresponding product N, N-dimethylglycine organic acid
  • the metal ion composite salt contains a metal ion which is a trivalent metal ion and may be selected from the group consisting of Al(III), Cr(III) or Fe(III).
  • the polyvalent metal halide reacted with the reaction solution in which the free form of DMG and the organic acid are uniformly mixed may be selected from the group consisting of polyvalent metal chlorides, polyvalent metal bromides, or polyvalent metal iodides.
  • the alkaline condition is that sufficient sodium hydroxide is added to the reaction system to adjust the pH of the reaction system to 7-8.
  • the polyvalent metal chloride is specifically copper chloride (CuCl 2 ), zinc chloride (ZnCl 2 ), manganese chloride (MnCl 2 ), ferrous chloride (FeCl 2 ), ferric chloride (FeCl 3 ).
  • the polyvalent metal bromide is specifically copper bromide (CuBr 2 ), zinc bromide (ZnBr 2 ), manganese bromide (MnBr 2 ), ferrous bromide (FeBr 2 ), iron bromide (FeBr 3 ). Chromium bromide (CrBr 2 ), chromium bromide (CrBr 3 ), cadmium bromide (CdBr 2 ), cobalt bromide (CoBr 2 ) or nickel bromide (NiBr 2 ).
  • the polyvalent metal iodide, copper bromide is particularly (CuI 2), zinc iodide (ZnI 2), manganese iodide (MnI 2), iron iodide (FeI 2), iron iodide (FeI 3) Chromium iodide (CrI 2 ), chromium iodide (CrI 3 ), cadmium iodide (CdI 2 ), cobalt iodide (CoI 2 ) or nickel iodide (NiI 2 ).
  • the corresponding product N,N-dimethylglycine organic acid polyvalent metal ion composite salt formed by the above process contains metal ions Cu(II), Zn(II), Fe(II), Mn(II), Cr ( II), Cd(II), Co(II), Ni(II), Cr(III) or Fe(III).
  • DMG hydrochloride is neutralized with anhydrous chemical equivalent sodium hydroxide in absolute ethanol to obtain free N,N-dimethylglycine, which is uniformly mixed with benzoic acid at normal temperature.
  • the liquid is further reacted with powdered calcium hydroxide to form a corresponding calcium complex salt of N,N-dimethylglycine benzoate.
  • the calcium complex salt of N,N-dimethylglycine benzoate comprises N,N-dimethylglycine ion, Ca(II) in an equivalent molar amount to the N,N-dimethylglycine ion and And a chemical equivalent of a benzoate ion such as the N,N-dimethylglycine ion and the Ca(II).
  • DMG hydrochloride is neutralized with anhydrous chemical equivalent sodium hydroxide in absolute ethanol to obtain free N,N-dimethylglycine, which is uniformly mixed with fumaric acid at normal temperature.
  • the reaction solution is further reacted with powdered calcium hydroxide to form a corresponding calcium, N,N-dimethylglycine fumarate complex salt.
  • the N,N-dimethylglycine calcium fumarate composite salt comprises N,N-dimethylglycine ion and Ca(II) in an equivalent molar amount to the N,N-dimethylglycine ion And a chemical equivalent of a fumarate ion such as the N,N-dimethylglycine ion and the Ca(II).
  • DMG hydrochloride is neutralized with anhydrous chemical equivalent sodium hydroxide in absolute ethanol to obtain free N,N-dimethylglycine, which is uniformly mixed with benzoic acid at normal temperature.
  • the liquid is further reacted with powdered copper hydroxide to form a corresponding copper complex salt of N,N-dimethylglycine benzoate.
  • the copper complex of N,N-dimethylglycine benzoate The salt comprises an N,N-dimethylglycine ion, an equivalent molar amount of Cu(II) and the N,N-dimethylglycine ion and the N,N-dimethylglycine ion A chemical equivalent of a benzoate ion such as Cu(II).
  • DMG hydrochloride is neutralized with anhydrous chemical equivalent sodium hydroxide in absolute ethanol to obtain free N,N-dimethylglycine, which is uniformly mixed with fumaric acid at normal temperature.
  • the reaction solution is further reacted with powdered copper hydroxide to form a corresponding copper complex salt of N,N-dimethylglycine fumarate.
  • the N,N-dimethylglycine copper fumarate composite salt comprises N,N-dimethylglycine ion and Cu(II) in an equivalent molar amount to the N,N-dimethylglycine ion And a chemical equivalent of the fumarate ion with the N,N-dimethylglycine ion and the Cu(II).
  • DMG hydrochloride is neutralized with anhydrous chemical equivalent sodium hydroxide in absolute ethanol to obtain free N,N-dimethylglycine, which is uniformly mixed with fumaric acid at normal temperature.
  • the reaction solution is further reacted with powdered zinc hydroxide to form a corresponding zinc complex salt of N,N-dimethylglycine fumarate.
  • the N,N-dimethylglycine zinc fumarate composite salt comprises N,N-dimethylglycine ion and an equivalent molar amount of Zn(II) with the N,N-dimethylglycine ion And a chemical equivalent of the fumarate ion with the N,N-dimethylglycine ion and the Zn(II).
  • DMG hydrochloride is neutralized with anhydrous chemical equivalent sodium hydroxide in absolute ethanol to obtain free N,N-dimethylglycine, which is uniformly mixed with benzoic acid at normal temperature.
  • the liquid is further reacted with powdered zinc hydroxide to form a corresponding zinc complex salt of N,N-dimethylglycine benzoate.
  • the zinc complex salt of N,N-dimethylglycine benzoate comprises an N,N-dimethylglycine ion, an equivalent molar amount of Zn(II) and the N,N-dimethylglycine ion and And a chemical equivalent of a benzoate ion such as the N,N-dimethylglycine ion and the Zn(II).
  • the present invention provides a process for preparing a N,N-dimethylglycine organic acid polyvalent metal ion complex salt, which further involves separation, purification or recrystallization of the reaction product.
  • the crude product is in an alcohol solvent, an alcohol-water mixed solvent or other organic solvent which can be used for product recrystallization.
  • the N,N-dimethylglycine organic acid polyvalent metal ion complex salt having a certain crystal form is recrystallized and separated under suitable conditions of temperature, illumination and mechanical vibration.
  • the N,N-dimethylglycine organic acid polyvalent metal ion complex salt having a certain crystal form may be a solvate thereof.
  • solvate means that in the process of contacting the complex salt of the present invention with a solvent molecule, external conditions and internal conditions cause a combination of chemically equivalent or non-stoichiometric solvent molecules by non-covalent intermolecular forces. A eutectic association formed. Solvents that form solvates include, but are not limited to, water, acetone, ethanol, methanol, dimethyl sulfoxide, ethyl acetate, acetic acid, isopropanol, and the like. "Hydrate” means a solvent or molecule that is an association or crystal formed by water, that is, a compound that combines a chemical equivalent or a non-stoichiometric amount of water by a non-covalent intermolecular force.
  • the solvate of the N,N-dimethylglycine organic acid polyvalent metal ion complex salt may be selected from a hydrate or an ethanolate of a N,N-dimethylglycine organic acid polyvalent metal ion complex salt.
  • the present invention provides a high-humidity stability study of the above-mentioned N,N-dimethylglycine organic acid polyvalent metal ion composite salt.
  • the N,N-dimethylglycine organic acid polyvalent metal ion composite salt was placed on the 10th day under the RH95% condition of 25 ° C.
  • the moisture absorption and weight increase are less than 5%, which is in line with the humidity requirement of the feed additive.
  • the present invention provides a feed composition comprising at least one of a N,N-dimethylglycine organic acid polyvalent metal ion complex salt or a solvate thereof provided by the present invention and a feedable auxiliary.
  • composition refers to a collective of compounds comprising one or more compounds which constitute an active ingredient.
  • the feedable auxiliary material comprises a feed additive or a carrier commonly used for the feed, a binder, an anti-caking agent, a stabilizer, an emulsifier, a diluent, a solvent or a combination thereof.
  • the “carrier” of the present invention means a feedable substance capable of supporting an active ingredient, improving dispersibility, and having good chemical stability and adsorption, and is classified into an organic vehicle and an inorganic carrier.
  • the organic carrier is generally a material containing a large amount of crude fiber, including but not limited to corn flour, corn cob powder, wheat bran, rice husk powder, defatted rice bran, taro, corn stalk powder, peanut shell powder and the like.
  • the inorganic carrier is generally a mineral, mainly divided into calcium salts and silicon oxides, used for the preparation of trace element premixes, including but not limited to calcium carbonate, silicate, vermiculite, zeolite, sea. Soapstone and so on.
  • the "diluent” referred to in the present invention refers to a substance in which the additive raw material is uniformly distributed in the material, and the high-concentration additive raw material is diluted into a low-concentration premix or premix, and the trace components can be separated from each other to reduce the active ingredient. The interaction between them increases the stability of the active ingredient without affecting the physicochemical properties of the substance.
  • the types of diluents are classified into organic diluents and inorganic diluents. Common organic diluents include, but are not limited to, corn flour, deblasted corn flour, dextrose (glucose), sucrose, semolina with bran, and fried soybeans. Powders, secondary powders, corn gluten meal, etc., commonly used inorganic diluents include, but are not limited to, limestone, calcium dihydrogen phosphate, shell powder, kaolin (white clay), salt and sodium sulfate.
  • Adjuvants to which the present invention relates include, but are not limited to, binders, wetting agents, disintegrants, lubricants, antioxidants, preservatives.
  • vehicle refers to a solvent required to dissolve or disperse a solid, including but not limited to water, ethanol, glycerol, and the like.
  • the forage composition comprises an additional animal feed additive, the additional animal feed addition being selected from the group consisting of a nutritive feed additive, a general feed additive or a pharmaceutical feed additive.
  • the nutritive feed additive includes, but is not limited to, an amino acid, an amino acid salt and the like, a vitamin and a vitamin, a mineral element and a chelating compound thereof, a microbial enzyme preparation or a non-protein nitrogen;
  • General feed Additives include, but are not limited to, growth promoters, insect repellents, flavoring and attractants, feed conditioners, feed conditioners, feed storage agents, and herbal additives;
  • the pharmaceutical feed additives include, but are not limited to, animals having prevention A veterinary drug premix that is diseased, promotes animal growth, and can be added to the feed for long-term use incorporation into a carrier or diluent.
  • the feed composition may comprise a feed material selected from the group consisting of non-feed additives, feed materials for animals, plants, microorganisms or minerals that can be used to process feed.
  • the feed composition is an additive premix feed, concentrate feed, compound feed, or concentrate supplement.
  • the feed additive premix feed refers to a nutritive feed additive of any two or more types of mineral trace elements, vitamins, microorganisms, and amino acids, and the butyrylglutamic acid derivative provided by the present invention. Or a homogeneous mixture of other feed additives, carriers and/or diluents in a proportion, wherein the content of the nutritive feed additive can meet the basic nutritional requirements of the particular physiological stage of the animal to be used in the compound feed, concentrate supplement or animal
  • the amount added in drinking water is not less than 0.1% and not more than 10%.
  • the concentrated feed refers to a feed mainly prepared with a certain proportion of protein, minerals and feed additives.
  • the compound feed refers to a feed prepared by a plurality of feed raw materials and feed additives according to a certain proportion according to the nutritional needs of the farmed animals.
  • the concentrate supplement refers to a feed prepared by supplementing a plurality of feed materials and feed additives according to a certain ratio in order to supplement the nutrition of the herbivore.
  • the invention also relates to a process for the preparation of the forage composition comprising the steps of weighing the raw materials and excipients, mixing the mixing unit, granulating, quality testing and packaging.
  • the present invention relates to the above-mentioned N,N-dimethylglycine organic acid polyvalent metal ion composite salt and a feed composition comprising the N,N-dimethylglycine organic acid polyvalent metal ion composite salt in the preparation of animal feed additives or Application in animal feed.
  • animal refers to a person who cannot synthesize inorganic substances into organic matter, and can only use organic matter as a food material for feeding, digesting, absorbing, breathing, circulating, excreting, feeling, exercising, and breeding as a living activity or breeding. animal.
  • farmed animals include poultry, livestock, aquatic animals, and other animals legally caught by captivity, including pets.
  • the poultry according to the present invention is a food-eating animal such as a chicken, a duck, a goose, a pigeon, a donkey or a turkey in each growth stage;
  • the livestock according to the present invention are pigs, cattle, sheep, rabbits at various growth stages, Food-eating animals such as horses;
  • the aquaculture animals involved in the present invention are fish, shrimp, loach, crab or cockroach in various growth stages; and the pets of the present invention include, but are not limited to, cats, dogs, rabbits and the like.
  • the N,N-dimethylglycine organic acid polyvalent metal ion composite salt provided by the invention is added to the basic diet of poultry such as chicken, duck, goose or pigeon, which can significantly reduce the ratio of meat to meat. Coefficient to increase the utilization of feed by poultry, The equivalent effect with sodium N,N-dimethylglycine is achieved.
  • the N,N-dimethylglycine organic acid polyvalent metal ion complex salt provided by the present invention is added to the basal diet of livestock such as pig, cow, sheep, etc., such as monogastric or ruminant, for livestock.
  • Production performance has a significant improvement, manifested by a decrease in average daily gain and average feed to meat ratio.
  • the addition of the N,N-dimethylglycine organic acid polyvalent metal ion complex salt provided by the present invention to the basic diet of aquaculture animals such as fish and shrimp can significantly improve aquaculture animals, especially Fish's ability to resist hypoxia increases survival.
  • the addition of the N,N-dimethylglycine organic acid copper salt provided by the present invention to the basal diet of the farmed animal improves the performance of the animal at a low dose to achieve high dose of inorganic copper to the animal.
  • the improvement in production performance improves the performance of the animal at a low dose to achieve high dose of inorganic copper to the animal. The improvement in production performance.
  • the addition of the N,N-dimethylglycine organic acid zinc salt provided by the present invention to the basal diet of the farmed animal significantly improves the performance of the animal.
  • N,N-dimethylglycine organic acid polyvalent metal ion complex salt can be used in combination with cat food, dog food and other pet rations to achieve the effect of regulating the gastrointestinal function of cats, dogs and other pets, effectively alleviating Pets have diarrhea due to indigestion.
  • the N,N-dimethylglycine organic acid polyvalent metal ion composite salt which is not easy to absorb moisture satisfies the requirements of the new feed additive for high humidity stability and has similar or superiority to N,N-dimethylglycine sodium.
  • the effect of improving the performance of farmed animals can be applied to the preparation of animal feed additives or animal feed.
  • N,N-dimethylglycine organic acid copper salt or the N,N-dimethylglycine organic acid zinc salt can be used as a substitute for high-dose inorganic copper and high-dose inorganic zinc in the feed additive or feed processing industry, respectively.
  • the product is used in the preparation of animal feed additives or animal feed.
  • the feed according to the present invention refers to a product that is industrially processed and produced for consumption by an animal.
  • Figure 1 is a flow chart showing the preparation process of a mixed pellet feed additive, and * indicates a critical control point.
  • Example 1 Calcium N,N-dimethylglycine benzoate, the chemical structural formula is as follows:
  • reaction solution was uniformly stirred at room temperature; 15.0 g (202.45 mmol, 1.01 eq) of powdered calcium hydroxide was put into the reaction system and stirred for 1 h to obtain a white viscous reaction liquid; 80 mL of absolute ethanol was added to the reaction system, The reaction mixture was stirred for 3 h to obtain a white suspension. The mixture was filtered under reduced pressure. The residue was washed with anhydrous ethanol (50 mL ⁇ 3) and dried under reduced pressure in an oven at 110 ° C overnight to give the title product as an off-white powder, yield 35.4 g, yield 67.1% .
  • the reaction mixture was filtered under reduced pressure to give a white solid.
  • the residue was washed with anhydrous ethanol (50mL ⁇ 3) and dried under vacuum at 50 ° C overnight to give a white solid.
  • the yield was 27.58 g, and the yield was 77.53%.
  • Example 10 N,N-dimethylglycine copper fumarate, the chemical formula is as follows:
  • the reaction mixture was filtered under reduced pressure to give a pale-yellow solid.
  • the residue was washed with anhydrous ethanol (50mL ⁇ 3) and dried under vacuum at 50 ° C overnight to give a white solid.
  • the yield was 32.64 g, yield 73.06%.
  • Sample 1 N,N-dimethylglycine hydrochloride, BEHRINGER TECHNOLOGY CO., LTD.;
  • Sample 2 sodium N,N-dimethylglycine, Shandong West Asia Chemical Industry Co., Ltd.;
  • Sample 8 N,N-dimethylglycine calcium fumarate, prepared in Example 4.
  • a saturated solution of KNO3 (25 ° C, RH 90%) was placed in the lower part of the constant temperature and humidity sealed container.
  • Three test samples were set in parallel for the test sample, and placed at 25 ° C, RH 95% ⁇ 1% for 10 days, on the 5th and 10th. The average weight of the test article is measured in days.
  • Sample 1 Sample 2 and Sample 3 are the hydrochloride, sodium and calcium salts of DMG, respectively.
  • the moisture absorption is very serious, and the water absorption of the test sample is carried out on the 5th day.
  • the sample is made to be watery.
  • Samples 6 and 7 are N,N-dimethylglycine calcium sulfate and N,N-dimethylglycine calcium phosphate, respectively. The moisture absorption and weight gain reached 60% to 65% on the 5th day, and the test sample was water. Sample.
  • Sample 5 and sample 8-14 belong to N,N-dimethylglycine organic acid calcium, N,N-dimethylglycine organic acid copper or N,N-dimethylglycine organic acid zinc, respectively. At 5 days, the moisture absorption did not exceed 3.6%, and there was no significant difference between the moisture absorption on the 5th and 10th days.
  • N,N-dimethylglycine organic acid polyvalent metal ion complex salt is kept at a constant temperature and humidity of 25 ° C, RH95% ⁇ 1% for 10 days, and the moisture absorption and weight increase are less than 5%, and it is relatively stable. Sex, in line with the humidity requirements of feed additives.
  • Sample 6 61.72 ⁇ 0.41 60.58 ⁇ 0.21 Sample 7 63.86 ⁇ 0.17 64.83 ⁇ 0.23 Sample 8 2.95 ⁇ 0.22 3.25 ⁇ 0.12 Sample 9 2.11 ⁇ 0.04 2.75 ⁇ 0.32 Sample 10 2.84 ⁇ 0.23 3.01 ⁇ 0.11 Sample 11 2.41 ⁇ 0.07 2.81 ⁇ 0.10 Sample 12 3.03 ⁇ 0.23 3.54 ⁇ 0.08 Sample 13 2.26 ⁇ 0.09 2.76 ⁇ 0.23 Sample 14 2.56 ⁇ 0.11 2.81 ⁇ 0.06
  • N,N-dimethylglycine organic acid polyvalent metal ion composite salts of Examples 1 to 10 were respectively mixed with corresponding auxiliary materials to prepare corresponding mixed pellet feed additives.
  • Raw materials N,N-dimethylglycine organic acid polyvalent metal ion complex salt of Examples 1 to 10, sodium N,N-dimethylglycinate;
  • Carrier corn starch
  • Binder 1.3% aqueous solution of hydroxypropylmethylcellulose.
  • Raw material supply R&D center of Guangzhou Instech Biotechnology Co., Ltd., which has passed the inspection by the Quality Control Department as a qualified product with a purity of ⁇ 99%.
  • Excipient purchase Purchasing excipients from qualified suppliers, and sampling after excipients to the factory. After passing the inspection, they can be put into storage and stored for standby. This process is a key control point, and the quality of excipients must be strictly controlled.
  • Production picking and weighing According to the proportion of the product formula, the raw materials and auxiliary materials are weighed and reviewed in turn, and the waste (packaging bags) produced are stored and treated uniformly.
  • Mixing Mix the raw materials and auxiliary materials into the mixing unit. This step is the key control point. The mixing time must be strictly controlled, and the mixing uniformity should be verified periodically.
  • the mixer is equipped with a pulse dust collector to reduce dust.
  • Granulation The product obtained by mixing the raw materials and auxiliary materials and the 1.3% aqueous solution of hydroxypropylmethylcellulose are put into the granulator according to the mass ratio of 100:35, and the mixing and cutting operation are started for 3-5 min. After the material is granulated, the granulation is carried out. It was dried in a fluidized bed and passed through a 16 mesh screen after 30 minutes.
  • Packing and inspection Weigh and package according to the packaging specifications, store in the finished product warehouse, identify the production batch and inspection status, etc. Each production batch is sampled at least two samples and sent to the laboratory for factory inspection and sample retention. After passing the inspection, it can be shipped. Thus, each mixed type pellet feed additive was obtained.
  • Production equipment cleaning After each batch of products is finished, the production area must be cleaned. When the production variety is replaced, the production equipment must be transported to remove impurities and prevent cross-contamination.
  • a single factor randomized design was used to select 1200 broiler broilers of 22 days old, with an average body weight of 153 g and similar body weight. They were randomly divided into 10 treatment groups, with 6 replicates in each group, half male and half female, and 20 replicates each. Three yellow feather broilers. Sterilize the house and utensils before the test. The trial period is carried out under the same feeding and management conditions in the same chicken house. The basal diet is dominated by corn-soybean meal, and no additional antioxidants or growth promoters are added throughout the feeding process. Each test group was a blank group, a control group, and a test group 1-8.
  • the blank group was given only the basal diet, the control group and the trial groups 1 to 8 respectively added 5000 ppm of the mixed pellet feed additive product provided by the present invention to the basal diet (see the section "Preparation method of feed composition").
  • the test chickens were given free access to water and food, and fed twice a day. Weighed at 42 days of age (12h, no water stop) in each repeat, the experimental chicken consumption was counted, and the average daily feed intake (ADFI) and average daily gain of each group of test chickens were calculated. ADG) and feed to meat ratio (FCR).
  • the experimental data were statistically analyzed using SPSS18 software. The data were analyzed by one-way analysis of variance (ANOVA).
  • test results are expressed as "mean ⁇ standard error", and the test results are shown in Table 4. From the results, we know that Compared with the control group, the feeds given by the control group had significant improvement effects on the feed intake, average daily gain and feed-to-meat ratio of the test chickens; the test groups 1-8 were compared with the blank control group. The feed intake of the test chickens was not significant, but the average daily gain was significantly increased while the feed-to-meat ratio was significantly decreased. The test group 1-8 was compared with the test results of the control group. The improvement in the ratio was not significant, but the feed-to-meat ratio of the test group 6-8 was significantly decreased.
  • the N,N-dimethylglycine benzoate, N,N-dimethylglycine fumarate, N,N-dimethyl Calcium citrate tetradecanoate and N,N-dimethylglycine p-toluenesulfonate have an aquaculture effect equivalent to N,N-dimethylglycine sodium salt, and the N,N-dimethyl provided by the present invention
  • the sodium glycinate salt has a better aquaculture effect, and the meat-to-meat ratio is reduced by about 11% compared with the experimental group which does not give any feed additive.
  • 270 heads of similarly-qualified 65-day-old Du Changda ternary heterozygous piglets were randomly divided into 9 treatment groups, with 3 replicates in each group, half male and half female, with 10 heads each.
  • the pigsty and utensils were sterilized before the test.
  • the test period is housed in the same breeding and management conditions under the same pig pen.
  • the test pigs were fed ad libitum and water, and fed twice a day.
  • Each test group was a control group and a test group of 1 to 10, respectively.
  • the control group was given only the basal diet, and the test groups 1 to 8 were respectively added with 1150 ppm of the mixed pellet feed additive products 1 to 13 provided by the present invention in the basal diet. No additional antioxidants and growth promoters were added to the test groups throughout the feeding process.
  • the test period is 28 days, and the productivity of the test pigs is counted in units of each repetition. Yes, average daily feed intake (ADFI), average daily gain (ADG), and feed to meat ratio (FCR).
  • the experimental data were statistically analyzed using SPSS18 software. The data were analyzed by one-way analysis of variance (ANOVA). If the difference between treatments was significant, Duncan's method was used for multiple comparisons, and the significance level was 0.05.
  • test results are expressed as "mean ⁇ standard error", and the test results are shown in Table 5. From the results, it was found that the test group fed the multivalent metal ion complex salt containing N,N-dimethylglycine organic acid had no significant effect on the feed intake of the test pigs, but the average daily gain was significant. The increase in the ratio of meat to meat decreased by 7.0% to 12.5%.
  • Test fish The test fish used was grass carp, and the fish species of the year were from the Dafeng fish farm in Huizhou City, Guangdong province. The healthy and lively, uniform-sized grass carp species were used for formal culture experiments after being kept in large cages (4 ⁇ 2 ⁇ 1.5m 3 ) for 4 weeks.
  • the experimental system was a floating small cage (size 1.1 ⁇ 1.1 ⁇ 1.1m 3 ). Each small cage is equipped with an inflatable head that inflates 24 hours a day. Both the small cage and the holding cage are placed in a 3500 m 2 pond at the test site. The pond has a water depth of about 1.5 m and the pond water is fully aerated.
  • Test feed The test feed was prepared according to the formula of Table 6. Different test groups were added with the same dose of different N,N-dimethylglycine organic acid polyvalent metal ion composite salt according to Table 7. The feed ingredients used were finely pulverized and then made into a floating bulking material with a particle size of 3 mm through a Jiangsu shepherd expansion unit. The mold temperature was 130 ° C, and 3% soybean oil was sprayed through the spray equipment, and sealed in a cool place for storage.
  • Raw material composition content(%) Raw material composition content(%) Fish meal 9.0 Soybean oil 3.0 Casing powder 3.0 Phospholipid 9.0 Cardamom 12.0 Gluten 4.0 Dish 12.0 Blood cell powder 2.0 Monosodium glutamate 3.0 Vc-phosphate 0.1 Secondary powder 12.6 Calcium dihydrogen phosphate 1.8 flour 17.0 Choline chloride 0.2 Bentonite 0.70 Multidimensional 0.1 Rice bran 10.0 Micro-mineral premix 0.5
  • Trial management The test was fed by artificial food restriction. The feeding amount was adjusted once a week. The feeding level of each group (according to the initial weight) was completely consistent and fed twice a day (7:30 and 15:00). The trial lasted for 8 weeks. The water quality was monitored regularly during the test. The whole process water temperature was 26.88 ⁇ 3.08°C, DO>5.0mg O L -1 , pH 7.8, ammonia nitrogen ⁇ 0.50mg N L -1 , nitrite nitrogen ⁇ 0.05mg N L -1 .
  • Weight gain rate 100 ⁇ (average final weight - average initial weight) / average initial weight;
  • Feed coefficient (FCR) food intake / fish weight gain
  • Survival rate (SR, %) 100 ⁇ number of fish at the end of the test / number of fish at the start of the test.
  • the control group was given only the basal diet, the proportion was given 2500 ppm of zinc oxide, and the test groups 1 to 6 were respectively given with different doses of the mixed granule feed additive product provided by the present invention in the basal diet, see Table 9.
  • No additional antioxidants and growth promoters were added to the test groups throughout the feeding process.
  • the test period was 15 days, and the performance of the test pigs was counted in units of each replicate, which were average daily feed intake (ADFI), average daily gain (ADG), and feed to meat ratio (FCR).
  • the experimental data were statistically analyzed using SPSS18 software. The data were analyzed by one-way analysis of variance (ANOVA).
  • the control group was given only the basal diet, the proportion was given 250 ppm of copper sulfate pentahydrate, and the test groups 1 to 4 were respectively given with different doses of the mixed pellet feed additive product provided by the present invention. See Table 10. No additional antioxidants and growth promoters were added to the test groups throughout the feeding process. The test period was 15 days, and the performance of the test pigs was counted in units of each replicate, which were average daily feed intake (ADFI), average daily gain (ADG), and feed to meat ratio (FCR). The experimental data were statistically analyzed using SPSS18 software. The data were analyzed by one-way analysis of variance (ANOVA).

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Abstract

本发明公开了一种N,N-二甲基甘氨酸有机酸多价金属离子复合盐或其溶剂合物及其在制备新型饲料添加剂和制备饲料中的应用；还公开了包含所述N,N-二甲基甘氨酸有机酸多价金属离子复合盐或其溶剂合物的饲用组合物。本发明提供的N,N-二甲基甘氨酸有机酸多价金属离子复合盐或其溶剂合物应用在动物养殖业中具有提高动物增重率、降低料肉比等动物生产性能的改善功效，与N,N-二甲基甘氨酸钠盐具有相似或更优的作用效果。

Description

N,N-二甲基甘氨酸有机酸复合盐及其组合物和应用 技术领域：
本发明属于动物饲料添加剂领域，具体涉及N,N-二甲基甘氨酸复合酸盐或其溶剂合物和包含前述盐的组合物及它们在制备动物饲料添加剂中的应用。
背景技术：
二甲基甘氨酸(Dimethylglycine，简称DMG)，分子式为(CH3)2NCH2COOH，外观白色结晶，溶于水和乙醇，是一种天然存在于食物、谷物豆类及肝脏中具有生理活性的营养物质，是动植物代谢途径的天然物质。二甲基甘氨酸作为一种营养抗氧化添加剂，在人和动物的健康上也显示出重要的生理生化功能。大量的动物试验发现二甲基甘酸是一种非常安全的食品类营养添加剂。
但是，N,N-二甲基甘氨酸是一种强吸湿性的固体，不方便储存和使用。常用的N,N-二甲基甘氨酸盐酸盐、N,N-二甲基甘氨酸钠、N,N-二甲基甘氨酸钾等的吸潮性也非常强，在储存中容易吸潮潮解，在产品加工中对生产设备和厂房设施要求高，否则将会导致生产过程中因吸潮而导致产品结块，达不到饲料加工业的应用要求。另外，含有DMG或DMG盐酸盐或碱金属盐的产品包装打包必须严格密封，一旦密封性不够产品在储存过程会因吸潮而导致产品霉变变质。
发明内容：
基于此，本发明提供一种不易吸潮的N,N-二甲基甘氨酸盐，所述的N,N-二甲基甘氨酸盐是一种N,N-二甲基甘氨酸有机酸多价金属离子复合盐或其溶剂合物，具有与N,N-二甲基甘氨酸钠等效或更优的改善动物生长性能的效果。特别的，本发明还提供了包含所述的N,N-二甲基甘氨酸有机酸多价金属离子复合盐或其溶剂合物的饲用组合物及其和所述的N,N-二甲基甘氨酸有机酸多价金属离子复合盐或其溶剂合物在制备动物饲料添加剂或动物饲料中的应用。
一方面，本发明提供了一种包含N,N-二甲基甘氨酸根离子、与所述N,N-二甲基甘氨酸根离子等摩尔量的多价金属离子和与所述N,N-二甲基甘氨酸根离子及所述多价金属离子等化学当量的饲料可接受的有机酸根离子的N,N-二甲基甘氨酸有机酸多价金属离子复合盐或其溶剂合物。
在一些实施方案中，所述与N,N-二甲基甘氨酸根离子等摩尔量的多价金属离子为二价金属离子或三价金属离子。
在一些实施方案中，所述的二价金属离子为碱土金属离子，可选自Ca(II)、Mg(II)、Ba(II) 或Sr(II)。
在一些实施方案中，所述的二价金属离子是过渡金属二价离子，可选自Cu(II)、Zn(II)、Fe(II)、Mn(II)、Cr(II)、Cd(II)、Co(II)或Ni(II)。
在一些实施方案中，所述的三价金属离子可选自Al(III)、Cr(III)或Fe(III)。
在一些实施方案中，所述的有机酸根离子对应的有机酸为多元有机酸，可选自富马酸、马来酸、酒石酸、琥珀酸、延胡索酸、丙二酸、苹果酸、二羟基丙酸、丙酮酸、乙醇酸、葡萄糖醛酸、半乳糖醛酸、天冬氨酸、谷氨酸、柠檬酸或草酸。
在一些实施方案中，所述的有机酸根离子对应的有机酸优选为富马酸。
在一些实施方案中，所述的有机酸根离子对应的有机酸为直链脂肪一元酸，可选自C4-C18直链脂肪一元酸。
在一些实施方案中，所述的有机酸根离子对应的有机酸为芳香有机酸，可选自苯甲酸、对甲苯甲酸、对氯苯甲酸、对溴苯甲酸、对氨基苯甲酸、扁桃酸、肉桂酸、苯磺酸、对甲苯磺酸、萘甲酸、水杨酸或乙酰水杨酸。
在一些实施方案中，所述的有机酸根离子对应的有机酸优选为苯甲酸或对甲苯甲酸。
在一些实施方案中，所述的N,N-二甲基甘氨酸有机酸多价金属离子复合盐包含N,N-二甲基甘氨酸根离子、与所述N,N-二甲基甘氨酸根离子相等摩尔量的Ca(II)和与所述N,N-二甲基甘氨酸根离子及所述Ca(II)等化学当量的苯甲酸根离子。
在一些实施方案中，所述的N,N-二甲基甘氨酸有机酸多价金属离子复合盐包含N,N-二甲基甘氨酸根离子、与所述N,N-二甲基甘氨酸根离子相等摩尔量的Ca(II)和与所述N,N-二甲基甘氨酸根离子及所述Ca(II)等化学当量的富马酸根离子。
在一些实施方案中，所述的N,N-二甲基甘氨酸有机酸多价金属离子复合盐包含N,N-二甲基甘氨酸根离子、与所述N,N-二甲基甘氨酸根离子相等摩尔量的Cu(II)和与所述N,N-二甲基甘氨酸根离子及所述Cu(II)等化学当量的苯甲酸根离子。
在一些实施方案中，所述的N,N-二甲基甘氨酸有机酸多价金属离子复合盐包含N,N-二甲基甘氨酸根离子、与所述N,N-二甲基甘氨酸根离子相等摩尔量的Cu(II)和与所述N,N-二甲基甘氨酸根离子及所述Cu(II)等化学当量的富马酸根离子。
在一些实施方案中，所述的N,N-二甲基甘氨酸有机酸多价金属离子复合盐包含N,N-二甲基甘氨酸根离子、与所述N,N-二甲基甘氨酸根离子相等摩尔量的Zn(II)和与所述N,N-二甲基甘氨酸根离子及所述Zn(II)等化学当量的苯甲酸根离子。
在一些实施方案中，所述的N,N-二甲基甘氨酸有机酸多价金属离子复合盐包含N,N-二甲 基甘氨酸根离子、与所述N,N-二甲基甘氨酸根离子相等摩尔量的Zn(II)和与所述N,N-二甲基甘氨酸根离子及所述Zn(II)等化学当量的富马酸根离子。
另一方面，本发明提供了一种饲用组合物，所述饲用组合物包含本发明提供的N,N-二甲基甘氨酸有机酸多价金属离子复合盐或其溶剂合物的至少一种和可饲用辅料。
可选的，所述的可饲用辅料为可饲用的载体、稀释剂、赋形剂、溶媒或它们的组合。
在一些实施方案中，所述的饲用组合物还包含饲料原料和或附加的动物饲料添加剂。
可选的，所述的附加的动物饲料添加剂为营养性饲料添加剂、一般饲料添加剂或药物饲料添加剂。
本发明提供了所述的N,N-二甲基甘氨酸有机酸多价金属离子复合盐或其溶剂合物的应用。
在一些实施方案中，所述的N,N-二甲基甘氨酸有机酸多价金属离子复合盐在制备动物饲料添加剂中的应用。
在一些实施方案中，所述的N,N-二甲基甘氨酸有机酸多价金属离子复合盐在制备动物饲料中的应用。
所述的动物为养殖动物，选自家畜、家禽、水产养殖动物或宠物。
本发明提供了包含N,N-二甲基甘氨酸有机酸多价金属离子复合盐或其溶剂合物的饲用组合物的应用。
在一些实施方案中，所述的饲用组合物在制备动物饲料添加剂中的应用。
在一些实施方案中，所述的饲用组合物在制备动物饲料中的应用。
所述的动物为养殖动物，选自家畜、家禽、水产养殖动物或宠物。
另一方面，本发明还提供了一种改善养殖动物生产性能的方法。
在一些实施方案中，所述的方法包括与饲料伴服的方式给予养殖动物本发明提供的N,N-二甲基甘氨酸有机酸多价金属离子复合盐或其溶剂合物。
在一些实施方案中，所述的方法包括给予养殖动物本发明提供的包含本发明提供的N,N-二甲基甘氨酸有机酸多价金属离子复合盐或其溶剂合物的饲用组合物。
另一方面，本发明还提供了所述N,N-二甲基甘氨酸有机酸多价金属离子复合盐的制备、分离和纯化方法。
本发明的有益效果：
本发明提供的N,N-二甲基甘氨酸有机酸多价金属离子复合盐是N,N-二甲基甘氨酸和有机酸同时与多价金属离子所成的盐，可降低N,N-二甲基甘氨酸的吸潮性。当所述N,N-二甲基甘氨酸有机酸多价金属离子复合盐或其溶剂合物应用在制备动物饲料添加剂或饲料中，由于 吸潮性的降低饲料或饲料添加剂的生产设备在防潮功能的要求下降，可降低生产成本。另外，产品的吸潮性降低对产品包装的密封性要求下降，成本降低的同时也可避免由于运输或存放过程的意外导致包装破损而带来的产品短期受潮变质的风险。
本发明提供的N,N-二甲基甘氨酸有机酸多价金属离子复合盐在养殖试验中，对家禽和家畜生产性能的改善效果与N,N-二甲基甘氨酸钠盐相当，部分盐甚至显示稍微更优的改善效果。
本发明的任一方面的任一实施方案可以与其他实施方案进行组合，只要它们之间不出现矛盾。此外，在本发明任一方面的任一实施方案中，任一技术特征可以适用于其它实施方案中的该技术特征，只要它们之间不会出现矛盾。
前面所述内容只是概述了本发明的某些方面，但不限于这些方面。上述涉及内容及其他方面的内容将在下面做更加具体完整的描述。
本发明的进一步详细描述。
现在详细描述本发明的某些实施方案，其实例由随附的结构式或化学式加以说明。本发明的意图涵盖所有的替代、修改和等同的技术方案，他们均包括在如权利要求定义的本发明的范围内。另外，本发明的某些技术特征为清楚可见，在多个独立的实施方案中分别进行描述，但也可以在单个实施例中以组合形式提供或以任意适合的组合形式提供。
本发明提供了一种包含N,N-二甲基甘氨酸根离子、与所述N,N-二甲基甘氨酸根离子等摩尔量的多价金属离子和与所述N,N-二甲基甘氨酸根离子及所述多价金属离子等化学当量的饲料可接受的有机酸根离子的N,N-二甲基甘氨酸有机酸多价金属离子复合盐。
本发明所述的“包含”为开放式表达，既包括本发明所明指的内容，但并不排除其他方面的内容。
本发明涉及的“多价金属离子”是指+2价或+3价的金属离子。
本发明涉及的“等摩尔量”是多价金属离子的数目与N,N-二甲基甘氨酸根离子的数目相等。
本发明涉及的“等化学当量”是指有机酸根离子的阴离子总价使得包含相同摩尔量的N,N-二甲基甘氨酸离子和多价金属离子的化学体呈现正负电荷平衡的电中性状态。
本发明涉及到的“饲料可接受的有机酸根离子”是指物质必须是适合化学或毒理学的，与组成的饲料或食用的养殖动物有关，对动物无毒的有机酸根离子。
本发明涉及的“复合盐”是指N,N-二甲基甘氨酸离子和另一种有机酸离子共同作为阴离子配体与金属离子组成的盐。
所述的N,N-二甲基甘氨酸有机酸多价金属离子复合盐的制备方法如下：
N,N-二甲基甘氨酸盐酸盐(简称DMG盐酸盐)在低级醇类有机溶剂中与等化学当量的 无机碱发生中和反应得游离型N,N-二甲基甘氨酸，在常温下与另一种有机酸混合均匀所得反应液进而与碱性多价金属氢氧化物或在碱性条件下与多价金属卤化物反应生成相应的N,N-二甲基甘氨酸有机酸多价金属离子复合盐，所述的“等化学当量”是指无机碱的用量可以使DMG盐酸盐游离得到DMG。
可选的，所述低级醇类有机溶剂为甲醇、乙醇、正丙醇、异丙醇或正丁醇。
在一些实施例中，所述的无机碱为氨水或碱金属的氢氧化物、碳酸盐或碳酸氢盐，包括但不限于氢氧化钠、氢氧化钾、碳酸钠、碳酸氢钠、碳酸钾和碳酸氢钾。
在一些实施例中，与游离型DMG混合均匀的另一种有机酸可选自多元有机酸、直链脂肪一元酸或芳香有机酸。
所述的多元有机酸可选自富马酸、马来酸、酒石酸、琥珀酸、延胡索酸、丙二酸、苹果酸、二羟基丙酸、丙酮酸、乙醇酸、葡萄糖醛酸、半乳糖醛酸、天冬氨酸、谷氨酸、柠檬酸或草酸，优选为富马酸。
所述的直链脂肪一元酸可选自C4-C18直链脂肪一元酸，优选为十四碳酸。
本发明涉及的“C4-C18直链脂肪一元酸”为含有碳原子数为4～18个的不带支链的脂肪一元酸。
所述的芳香有机酸可选自苯甲酸、对甲苯甲酸、对氯苯甲酸、对溴苯甲酸、对氨基苯甲酸、扁桃酸、肉桂酸、苯磺酸、对甲苯磺酸、萘甲酸、水杨酸或乙酰水杨酸，优选为苯甲酸、对甲苯甲酸或对甲苯磺酸。
在一些实施例中，与游离型DMG和所述有机酸混合均匀的反应液反应的碱性多价金属氢氧化物可选自碱性二价金属氢氧化物或碱性三价金属氢氧化物。
可选的，所述的碱性二价金属氢氧化物为碱土金属氢氧化物。具体的，所述的碱土金属氢氧化物为氢氧化钙(Ca(OH)2)、氢氧化镁(Mg(OH)2)、氢氧化钡(Ba(OH)2)或氢氧化锶(Sr(OH)2)，相应的产物N,N-二甲基甘氨酸有机酸多价金属离子复合盐包含的金属离子为二价的碱土金属离子，可选自Ca(II)、Mg(II)、Ba(II)或Sr(II)。
进一步可选的，所述的碱性二价金属氢氧化物为碱性过渡金属氢氧化物。具体的，所述的碱性过渡金属氢氧化物为氢氧化铜(Cu(OH)2)、氢氧化锌(Zn(OH)2)、氢氧化亚铁(Fe(OH)2)、氢氧化镉(Cd(OH)2)、氢氧化钴(Co(OH)2)或氢氧化镍(Ni(OH)2)，相应的产物N,N-二甲基甘氨酸有机酸多价金属离子复合盐包含的金属离子为过渡金属二价离子，可选自Cu(II)、Zn(II)、Fe(II)、Cd(II)、Co(II)或Ni(II)。
在一些实施例中，与游离型DMG和所述有机酸混合均匀的反应液反应的碱性多价金属 氢氧化物为碱性三价金属氢氧化物，所述的碱性三价金属氢氧化物优选为氢氧化铁(Fe(OH)3)、氢氧化铬(Cr(OH)3)或氢氧化铝(Al(OH)3)，相应的产物N,N-二甲基甘氨酸有机酸多价金属离子复合盐包含的金属离子为三价金属离子，可选自Al(III)、Cr(III)或Fe(III)。
在一些实施例中，与游离型DMG和所述有机酸混合均匀的反应液反应的多价金属卤化物可选自多价金属氯化物、多价金属溴化物或多价金属碘化物。
所述的碱性条件为在反应体系中加入足够的氢氧化钠使反应体系pH为7～8。
所述的多价金属氯化物具体为氯化铜(CuCl2)、氯化锌(ZnCl2)、氯化锰(MnCl2)、氯化亚铁(FeCl2)、氯化铁(FeCl3)、氯化亚铬(CrCl2)、氯化铬(CrCl3)、氯化镉(CdCl2)、氯化钴(CoCl2)或氯化镍(NiCl2)。
所述的多价金属溴化物具体为溴化铜(CuBr2)、溴化锌(ZnBr2)、溴化锰(MnBr2)、溴化亚铁(FeBr2)、溴化铁(FeBr3)、溴化铬(CrBr2)、溴化铬(CrBr3)、溴化镉(CdBr2)、溴化钴(CoBr2)或溴化镍(NiBr2)。
所述的多价金属碘化物具体为溴化铜(CuI2)、碘化锌(ZnI2)、碘化锰(MnI2)、碘化亚铁(FeI2)、碘化铁(FeI3)、碘化铬(CrI2)、碘化铬(CrI3)、碘化镉(CdI2)、碘化钴(CoI2)或碘化镍(NiI2)。
上述过程生成的相应的产物N,N-二甲基甘氨酸有机酸多价金属离子复合盐包含的金属离子为Cu(II)、Zn(II)、Fe(II)、Mn(II)、Cr(II)、Cd(II)、Co(II)、Ni(II)、Cr(III)或Fe(III)。
在一具体实施例中，DMG盐酸盐在无水乙醇中与等化学当量的氢氧化钠发生中和反应得游离型N,N-二甲基甘氨酸，在常温下与苯甲酸混合均匀所得反应液进而与粉末状的氢氧化钙反应生成相应的N,N-二甲基甘氨酸苯甲酸钙复合盐。所述的N,N-二甲基甘氨酸苯甲酸钙复合盐包含N,N-二甲基甘氨酸根离子、与所述N,N-二甲基甘氨酸根离子相等摩尔量的Ca(II)和与所述N,N-二甲基甘氨酸根离子及所述Ca(II)等化学当量的苯甲酸根离子。
在一具体实施例中，DMG盐酸盐在无水乙醇中与等化学当量的氢氧化钠发生中和反应得游离型N,N-二甲基甘氨酸，在常温下与富马酸混合均匀所得反应液进而与粉末状的氢氧化钙反应生成相应的N,N-二甲基甘氨酸富马酸钙复合盐。所述的N,N-二甲基甘氨酸富马酸钙复合盐包含N,N-二甲基甘氨酸根离子、与所述N,N-二甲基甘氨酸根离子相等摩尔量的Ca(II)和与所述N,N-二甲基甘氨酸根离子及所述Ca(II)等化学当量的富马酸根离子。
在一具体实施例中，DMG盐酸盐在无水乙醇中与等化学当量的氢氧化钠发生中和反应得游离型N,N-二甲基甘氨酸，在常温下与苯甲酸混合均匀所得反应液进而与粉末状的氢氧化铜反应生成相应的N,N-二甲基甘氨酸苯甲酸铜复合盐。所述的N,N-二甲基甘氨酸苯甲酸铜复合 盐包含N,N-二甲基甘氨酸根离子、与所述N,N-二甲基甘氨酸根离子相等摩尔量的Cu(II)和与所述N,N-二甲基甘氨酸根离子及所述Cu(II)等化学当量的苯甲酸根离子。
在一具体实施例中，DMG盐酸盐在无水乙醇中与等化学当量的氢氧化钠发生中和反应得游离型N,N-二甲基甘氨酸，在常温下与富马酸混合均匀所得反应液进而与粉末状的氢氧化铜反应生成相应的N,N-二甲基甘氨酸富马酸铜复合盐。所述的N,N-二甲基甘氨酸富马酸铜复合盐包含N,N-二甲基甘氨酸根离子、与所述N,N-二甲基甘氨酸根离子相等摩尔量的Cu(II)和与所述N,N-二甲基甘氨酸根离子及所述Cu(II)等化学当量的富马酸根离子。
在一具体实施例中，DMG盐酸盐在无水乙醇中与等化学当量的氢氧化钠发生中和反应得游离型N,N-二甲基甘氨酸，在常温下与富马酸混合均匀所得反应液进而与粉末状的氢氧化锌反应生成相应的N,N-二甲基甘氨酸富马酸锌复合盐。所述的N,N-二甲基甘氨酸富马酸锌复合盐包含N,N-二甲基甘氨酸根离子、与所述N,N-二甲基甘氨酸根离子相等摩尔量的Zn(II)和与所述N,N-二甲基甘氨酸根离子及所述Zn(II)等化学当量的富马酸根离子。
在一具体实施例中，DMG盐酸盐在无水乙醇中与等化学当量的氢氧化钠发生中和反应得游离型N,N-二甲基甘氨酸，在常温下与苯甲酸混合均匀所得反应液进而与粉末状的氢氧化锌反应生成相应的N,N-二甲基甘氨酸苯甲酸锌复合盐。所述的N,N-二甲基甘氨酸苯甲酸锌复合盐包含N,N-二甲基甘氨酸根离子、与所述N,N-二甲基甘氨酸根离子相等摩尔量的Zn(II)和与所述N,N-二甲基甘氨酸根离子及所述Zn(II)等化学当量的苯甲酸根离子。
在一些实施例中，本发明提供N,N-二甲基甘氨酸有机酸多价金属离子复合盐的制备过程还涉及反应产物的分离、纯化或重结晶过程。为了获得化学纯度更高、杂质含量更低的N,N-二甲基甘氨酸有机酸多价金属离子复合盐，粗品经醇溶剂、醇水混合溶剂或其他可用于产品重结晶的有机溶剂中在合适的温度、光照以及机械振动等条件下重结晶和分离得到具有一定晶型状态的N,N-二甲基甘氨酸有机酸多价金属离子复合盐。所述具有一定晶型状态的N,N-二甲基甘氨酸有机酸多价金属离子复合盐可以是其溶剂合物。
本发明涉及的“溶剂合物”是指本发明的复合盐与溶剂分子接触的过程中，外部条件与内部条件因素造成通过非共价分子间力而结合化学当量或非化学当量的溶剂分子而形成的共晶缔合物。形成溶剂合物的溶剂包括但是不限于水、丙酮、乙醇、甲醇、二甲亚砜、乙酸乙酯、乙酸、异丙醇等溶剂。“水合物”是指溶剂分子是水所形成的缔合物或结晶体，也就是通过非共价分子间力而结合化学当量或非化学当量的水的化合物。
所述的N,N-二甲基甘氨酸有机酸多价金属离子复合盐的溶剂合物可选自N,N-二甲基甘氨酸有机酸多价金属离子复合盐的水合物或乙醇合物。
本发明提供了上述N,N-二甲基甘氨酸有机酸多价金属离子复合盐的高湿稳定性研究。在新饲料添加剂稳定性试验规范要求的高湿稳定性试验研究中，所述的N,N-二甲基甘氨酸有机酸多价金属离子复合盐在25℃的RH95％条件下放置到第10天吸湿增重量均低于5％，符合饲料添加剂的对湿度的要求。
本发明提供一种饲用组合物，包含本发明提供的N,N-二甲基甘氨酸有机酸多价金属离子复合盐或其溶剂合物的至少一种和可饲用辅料。
本发明涉及的“组合物”是指包含一种或一种以上的化合物组成有效成分的化合物集体。
本发明所述的“包含”为开放式表达，既包括本发明所明指的内容，但并不排除其他方面的内容。
可选的，所述可饲用辅料包括饲料添加剂或饲料常用的载体、粘结剂、抗结块剂、稳定剂、乳化剂、稀释剂、溶媒或它们的组合。
本发明的“载体”是指能够承载活性成分，改善其分散性，并有良好的化学稳定性和吸附性的可饲用物质，分为有机载体和无机载体。所述的有机载体般是含粗纤维多的物料，包括但不限于玉米粉、玉米芯粉、麦麸、稻壳粉、脱脂米糠、统糠、玉米秸秆粉、花生壳粉等。所述的无机载体一般是矿物质，主要分为钙盐类和硅的氧化物类，用于微量元素预混料的制作，包括但不限于碳酸钙、硅酸盐、蛭石、沸石、海泡石等。
本发明涉及的“稀释剂”是指将添加剂原料均匀分布于物料中，将高浓度的添加剂原料稀释为低浓度的预混剂或预混料的物质，可将微量成分彼此分开，减少活性成分之间的相互反应，以增加活性成分的稳定性但不影响有关物质的物化性质。稀释剂的种类分为有机稀释剂和无机稀释剂，常见的有机稀释剂包括但不限于玉米粉、去胚玉米粉、右旋糖(葡萄糖)、蔗糖、带有麸皮的粗小麦粉、炒大豆粉、次粉、玉米蛋白粉等，常用的无机稀释剂包括但不限于石灰石、磷酸二氢钙、贝壳粉、高岭土(白陶土)、食盐和硫酸钠。
本发明涉及的辅剂包括但不限于指粘合剂、润湿剂、崩解剂、润滑剂、抗氧化剂、防腐剂。
本发明涉及的“媒介物”是指溶解或分散固体所需的溶剂，包括但不限于水、乙醇、甘油等。
进一步的，所述的饲用组合物包含附加的动物饲料添加剂，所述的附加的动物饲料添加选自营养性饲料添加剂、一般性饲料添加剂或药物饲料添加剂。
具体的，所述的营养性饲料添加剂包括但不限于氨基酸、氨基酸盐及其类似物、维生素及类维生素、矿物元素及其络(螯)合物、微生物酶制剂或非蛋白氮；所述的一般性饲料添 加剂包括但不限于生长促进剂、驱虫保健剂、调味和诱食剂、饲料调质剂、饲料调制剂、饲料贮藏剂和中草药添加剂；所述的药物饲料添加剂包括但不限于具有预防动物疾病、促进动物生长作用并可在饲料中长期添加使用而掺入载体或稀释剂的兽药预混合物质。
进一步的，所述的饲用组合物可包含饲料原料，所述的饲料原料选自非饲料添加剂的可用于加工制作饲料的动物、植物、微生物或矿物等饲用物质。
在一些实施方案中，所述饲用组合物为添加剂预混合饲料、浓缩饲料、配合饲料或精料补充料。
所述的饲料添加剂预混合饲料，是指以矿物质微量元素、维生素、微生物、氨基酸中任何两类或两类以上的营养性饲料添加剂为主，与本发明提供的丁酰谷氨酸衍生物或其他饲料添加剂、载体和(或)稀释剂按照一定比例配制的均匀混合物，其中营养性饲料添加剂的含量能够满足其适用动物特定生理阶段的基本营养需求，在配合饲料、精料补充料或动物饮用水中的添加量不低于0.1％且不高于10％。
所述的浓缩饲料是指主要有蛋白质、矿物质和饲料添加剂按照一定比例配制的饲料。
所述的配合饲料是指根据养殖动物营养需要，将多种饲料原料和饲料添加剂按照一定比例配制的饲料。
所述的精料补充料是指为补充草食动物的营养，将多种饲料原料和饲料添加剂按照一定比例配制的饲料。
本发明还涉及所述饲用组合物的制备过程，包括称重原料和辅料、混合机组混合、制粒、质检和包装的过程。
本发明涉及上述N,N-二甲基甘氨酸有机酸多价金属离子复合盐及包含N,N-二甲基甘氨酸有机酸多价金属离子复合盐的饲用组合物的在制备动物饲料添加剂或动物饲料中的应用。
本发明涉及的“动物”是指不能将无机物合成有机物，只能以有机物作为食料，以进行摄食、消化、吸收、呼吸、循环、***、感觉、运动和繁殖等为生命活动的人或养殖动物。
可选的，养殖动物包括家禽、家畜、水产动物以及人工饲养合法捕获的其他动物包括宠物。具体的，本发明涉及的家禽为各个生长阶段的鸡、鸭、鹅、鸽、鹌鹑或火鸡等食源性动物；本发明涉及的家畜为各个生长阶段的猪、牛、羊、家兔、马等食源性动物；本发明涉及的水产养殖动物为各个生长阶段的鱼、虾、泥鳅、蟹或鳝等；本发明涉及的宠物包括但不限于猫、狗、兔等。
在一些养殖方案中，在鸡、鸭、鹅或鸽等家禽的基础日粮中添加本发明提供的N,N-二甲基甘氨酸有机酸多价金属离子复合盐，可显著的降低料肉比系数，提高家禽对饲料的利用率， 达到与N,N-二甲基甘氨酸钠的等效的作用效果。
在一些养殖方案中，在猪、牛、羊等单胃的或反刍等家畜的基础日粮中添加本发明提供的N,N-二甲基甘氨酸有机酸多价金属离子复合盐，对家畜的生产性能具有显著的改善作用，表现在平均日增重和平均料肉比的下降。
在一些养殖方案中，在鱼、虾等水产养殖动物的基础日粮中添加本发明提供的N,N-二甲基甘氨酸有机酸多价金属离子复合盐，可显著的改善水产养殖动物尤其是鱼类的抗缺氧能力提高存活率。
在一些养殖方案中，在养殖动物的基础日粮中添加本发明提供的N,N-二甲基甘氨酸有机酸铜盐对动物生产性能的改善效果在低剂量时可达到高剂量无机铜对动物生产性能的改善效果。
在一些养殖方案中，在养殖动物的基础日粮中添加本发明提供的N,N-二甲基甘氨酸有机酸锌盐在显著提高动物的生产性能。
在一些养殖方案中，N,N-二甲基甘氨酸有机酸多价金属离子复合盐可与猫粮、狗粮等宠物口粮联合使用，达到调节猫、狗等宠物的肠胃功能的功效，有效缓解宠物因消化不良导致的拉稀症状。
因此，不易吸潮的N,N-二甲基甘氨酸有机酸多价金属离子复合盐满足新饲料添加剂对高湿稳定性的要求还具有与N,N-二甲基甘氨酸钠相似或更优的改善养殖动物生产性能的效果，可应用在制备动物饲料添加剂或动物饲料中。
进一步的，N,N-二甲基甘氨酸有机酸铜盐或N,N-二甲基甘氨酸有机酸锌盐在饲料添加剂或饲料加工业中可分别作为高剂量无机铜和高剂量无机锌的替代品应用在制备动物饲料添加剂或动物饲料中。
本发明涉及的饲料是指经工业化加工、制作的供动物食用的产品。
附图说明
图1是混合型颗粒饲料添加剂的制备工艺流程图，*表示关键控制点。
具体实施方式：
为了使本发明的目的、技术方案及优点更加清楚明白，以下通过实施例对本发明的化合物、组合物及应用进行进一步的详细说明。应当理解，此处所描述的具体实施例仅用于解释本发明，并不用于限定本发明。
一、N,N-二甲基甘氨酸有机酸多价金属离子复合盐的制备：
实施例1 N,N-二甲基甘氨酸苯甲酸钙，化学结构式如下：
Figure PCTCN2017107673-appb-000001
1L三口反应烧瓶中依次加入N,N-二甲基甘氨酸盐酸盐(简称DMG盐酸盐)28.00g(200.60mmol，1.00eq)，无水乙醇350mL，室温下剧烈搅拌形成均匀混悬液；反应体系中分批加入固体氢氧化钠8.2g(1g×8，205.0mmol，1.02eq)，放热，室温搅拌反应0.5h；反应体系加入针状结晶固体苯甲酸25.0g(204.7mmol，1.02eq)，室温剧烈搅拌使反应液分散均匀；粉末状氢氧化钙15.0g(202.45mmol，1.01eq)投入反应体系搅拌反应1h得白色粘稠性反应液；往反应体系中加入80mL无水乙醇，剧烈搅拌反应3h得白色混悬液，减压抽滤，滤渣经无水乙醇(50mL×3)洗涤后在110℃烘箱减压干燥过夜得题述产物为灰白色粉末，产量35.4g，收率67.1％。
1HNMR(400MHz,D2O):δ(ppm)2.13(s,6H),2.82(s,2H),7.27-7.39(m,3H),8.01-8.03(m,2H).
实施例2 N,N-二甲基甘氨酸硫酸钙，化学式结构式如下：
Figure PCTCN2017107673-appb-000002
在300mL无水乙醇中加入DMG盐酸盐28.00g(200.60mmol，1.00eq)，室温下剧烈搅拌形成均匀混悬液；反应体系中分批加入固体氢氧化钠8.2g(1g×8，205.0mmol，1.02eq)，放热，室温搅拌反应0.5h；反应液冷却至-20℃，剧烈搅拌下缓慢滴加浓硫酸9.84g(100.30mmol，0.50eq)，滴毕反应液升温至室温后加入粉末状氢氧化钙15.0g(202.45mmol，1.01eq)搅拌反应1h得乳状粘稠性反应液；往反应体系中加入80mL无水乙醇，剧烈搅拌反应3h得白色混悬液，减压抽滤，滤渣经无水乙醇(50mL×3)洗涤后在110℃烘箱减压干燥过夜得题述产物为白色固体，产量23.36g，收率为83.67％。
实施例3 N,N-二甲基甘氨酸磷酸钙，化学式结构式如下：
Figure PCTCN2017107673-appb-000003
在300mL无水乙醇中加入DMG盐酸盐28.00g(200.60mmol，1.00eq)，剧烈搅拌下加入固体NaOH 8.02g(200.60mmol，1.00eq)，剧烈放热，室温下缓慢滴加85％磷酸7.86g(68.20mmol，0.34eq)，滴毕反应液中加入固体Ca(OH)215.00g(202.45mmol，1.00eq)，反应液在室温下搅拌 1小时后得一乳状液。往乳状反应液中加入100mL无水乙醇，继续搅拌反应3小时。反应液经减压抽滤得滤渣为白色固体，滤渣经无水乙醇(50mL×3)洗涤后50℃下真空干燥过夜得产物为白色固体，产量27.58g，收率为77.53％。
实施例4 N,N-二甲基甘氨酸富马酸钙，化学式结构式如下：
Figure PCTCN2017107673-appb-000004
在300mL无水乙醇中加入DMG盐酸盐28.00g(200.60mmol，1.00eq)，剧烈搅拌下加入固体NaOH 8.02g(200.60mmol，1.00eq)，剧烈放热，室温下往反应液中依次加入富马酸11.64g(100.30mmol，0.50eq)和固体Ca(OH)215.00g(202.45mmol，1.00eq)，反应液在室温下搅拌1小时后得一乳状液。往乳状反应液中加入100mL无水乙醇，继续搅拌反应3小时。反应液经减压抽滤得滤渣为白色固体，滤渣经无水乙醇(50mL×3)洗涤后50℃下真空干燥过夜得产物为白色固体，产量27.66g，收率为69.21％。
1HNMR(400MHz,DMSO-d6):δ(ppm)2.22(s,6H),2.97(s,2H),6.50(s,2H).
实施例5 N,N-二甲基甘氨酸十四酸钙，化学式结构式如下：
Figure PCTCN2017107673-appb-000005
在300mL无水乙醇中加入DMG盐酸盐28.00g(200.60mmol，1.00eq)，剧烈搅拌下加入固体NaOH 8g(200.01mmol，1.00eq)，剧烈放热，室温下继续搅拌0.5小时后依次十四酸45.81g(200.60mmol，1.00eq)和固体Ca(OH)2 15.00g(202.45mmol，1.01eq)，反应液在室温下搅拌1小时后得一乳状液。往乳状反应液中加入100mL无水乙醇，继续搅拌反应3小时。反应液经减压抽滤得滤渣为白色固体，滤渣经无水乙醇(100mL×3)洗涤后50℃下真空干燥过夜得产物为白色固体，产量62.52g，收率为84.33％。
实施例6 N,N-二甲基甘氨酸对甲苯磺酸钙，化学式结构式如下：
Figure PCTCN2017107673-appb-000006
在300mL无水乙醇中加入DMG盐酸盐28.00g(200.60mmol，1.00eq)，剧烈搅拌下加入固体NaOH 8g(200.01mmol，1.00eq)，剧烈放热，室温下继续搅拌0.5小时后依次对甲苯磺酸34.50g(200.35mmol，1.00eq)和固体Ca(OH)2 15.00g(202.45mmol，1.01eq)，反应液在室温下 搅拌1小时后得一乳状液。往乳状反应液中加入100mL无水乙醇，继续搅拌反应3小时。反应液经减压抽滤得滤渣为白色固体，滤渣经无水乙醇(50mL×3)洗涤后50℃下真空干燥过夜得产物为白色固体，产量46.66g，收率为74.23％。
实施例7 N,N-二甲基甘氨酸苯甲酸铜，化学式结构式如下：
Figure PCTCN2017107673-appb-000007
1L三口反应烧瓶中依次加入DMG盐酸盐28.00g(200.60mmol，1.00eq)，无水乙醇350mL，室温下剧烈搅拌形成均匀混悬液；反应体系中分批加入固体氢氧化钠8.03g(1g×8，200.76mmol，1.00eq)，放热，室温搅拌反应0.5h；反应体系加入针状结晶固体苯甲酸24.50g(200.60mmol，1.00eq)，室温剧烈搅拌使反应液分散均匀；粉末状氢氧化铜19.57g(200.60mmol，1.00eq)投入反应体系搅拌反应1h得浅蓝色粘稠性反应液；往反应体系中加入80mL无水乙醇，剧烈搅拌反应3h得浅蓝色混悬液，减压抽滤，滤渣经无水乙醇(50mL×3)洗涤后在110℃烘箱减压干燥过夜得题述产物为白色细沙状粉末，产量34.14g，收率59.34％。
实施例8 N,N-二甲基甘氨酸苯甲酸锌，化学式结构式如下：
Figure PCTCN2017107673-appb-000008
反应器中依次加入DMG盐酸盐28.00g(200.60mmol，1.00eq)，无水乙醇350mL，室温下剧烈搅拌形成均匀混悬液；反应体系中分批加入固体氢氧化钠8.03g(1g×8，200.76mmol，1.00eq)，放热，室温搅拌反应0.5h；反应体系加入针状结晶固体苯甲酸24.50g(200.60mmol，1.00eq)，室温剧烈搅拌使反应液分散均匀；粉末状氢氧化锌19.57g(200.60mmol，1.00eq)投入反应体系搅拌反应1h得白色稠性反应液；往反应体系中加入80mL无水乙醇，剧烈搅拌反应3h得白色混悬液，减压抽滤，滤渣经无水乙醇(50mL×3)洗涤后在110℃烘箱减压干燥过夜得题述产物为白色粉末，产量31.06g，收率53.65％。
实施例9 N,N-二甲基甘氨酸富马酸锌，化学式结构式如下：
Figure PCTCN2017107673-appb-000009
在300mL无水乙醇中加入DMG盐酸盐28.00g(200.60mmol，1.00eq)，剧烈搅拌下加入固体NaOH 8.02g(200.60mmol，1.00eq)，剧烈放热，室温下往反应液中依次加入富马酸11.64g (100.30mmol，0.50eq)和固体Zn(OH)220.00g(201.22mmol，1.00eq)，反应液在室温下搅拌1小时后得一乳状液。往乳状反应液中加入100mL无水乙醇，继续搅拌反应3小时。反应液经减压抽滤得滤渣为白色固体，滤渣经无水乙醇(50mL×3)洗涤后50℃下真空干燥过夜得产物为白色固体，产量24.16g，收率为53.65％。
实施例10 N,N-二甲基甘氨酸富马酸铜，化学式结构式如下：
Figure PCTCN2017107673-appb-000010
在300mL无水乙醇中加入DMG盐酸盐28.00g(200.60mmol，1.00eq)，剧烈搅拌下加入固体NaOH 8.02g(200.60mmol，1.00eq)，剧烈放热，室温下往反应液中依次加入富马酸11.64g(100.30mmol，0.50eq)和固体Zn(OH)2 19.60g(200.60mmol，1.00eq)，反应液在室温下搅拌1小时后得一乳状液。往乳状反应液中加入100mL无水乙醇，继续搅拌反应3小时。反应液经减压抽滤得滤渣为淡蓝色固体，滤渣经无水乙醇(50mL×3)洗涤后50℃下真空干燥过夜得产物为白色固体，产量32.64g，收率为73.06％。
二、N,N-二甲基甘氨酸有机酸多价金属离子复合盐的相关性质
供试品及供应商：
样品1：N,N-二甲基甘氨酸盐酸盐，百灵威科技有限公司；
样品2：N,N-二甲基甘氨酸钠，山东西亚化学工业有限公司；
样品3：N,N-二甲基甘氨酸钙，广州英赛特生物技术有限公司研发中心；
样品4：苯甲酸钙，广州英赛特生物技术有限公司研发中心；
样品5：N,N-二甲基甘氨酸苯甲酸钙，实施例1制备；
样品6：N,N-二甲基甘氨酸硫酸钙，实施例2制备；
样品7：N,N-二甲基甘氨酸磷酸钙，实施例3制备；
样品8：N,N-二甲基甘氨酸富马酸钙，实施例4制备；
样品9：N,N-二甲基甘氨酸十四酸钙，实施例5制备；
样品10：N,N-二甲基甘氨酸对甲苯磺酸钙，实施例6制备；
样品11：N,N-二甲基甘氨酸苯甲酸铜，实施例7制备；
样品12：N,N-二甲基甘氨酸苯甲酸锌，实施例8制备；
样品13：N,N-二甲基甘氨酸富马酸锌，实施例9制备；
样品14：N,N-二甲基甘氨酸富马酸铜，实施例10制备；
1、性状及熔点测定
表1 N,N-二甲基甘氨酸有机酸多价金属离子复合盐的性状及熔点测定
供试品 性状 熔点/℃
N,N-二甲基甘氨酸盐酸盐 白色结晶状颗粒 189-193
N,N-二甲基甘氨酸钠 白色粉末 217℃
N,N-二甲基甘氨酸钙 白色粉末 220℃，未溶解，分解
苯甲酸钙 白色粉末 ﹥260℃，未溶解，未分解
样品5 白色粉末 ﹥240℃，未溶解，分解
2、高湿稳定性试验
方法：
恒温恒湿密闭容器下部放置KNO3饱和溶液(25℃，RH90％)，供试品平行设置三个检测样品，于25℃、RH95％±1％条件下放置10天，于第5天和第10天检测供试品的平均增重量。
结果：试验数据采用SPSS18软件进行统计分析，试验结果以“平均值±标准误”表示如表2所示。在25℃下的RH95％条件下，样品1、样品2和样品3分别为DMG的盐酸盐、钠盐和钙盐，吸潮性非常严重，实验进行到第5天供试品的吸水量达到使样品成为水样状。样品6和样品7分别是N,N-二甲基甘氨酸硫酸钙和N,N-二甲基甘氨酸磷酸钙，吸潮增重量在第5天时达到了60％～65％，供试品为水样状。样品5、样品8-14分别属于N,N-二甲基甘氨酸有机酸钙、N,N-二甲基甘氨酸有机酸铜或N,N-二甲基甘氨酸有机酸锌，在试验进行到第5天时吸湿增重量不超过3.6％，并且第5天与第10天的吸潮增重量没有显著的区别。
结论：N,N-二甲基甘氨酸有机酸多价金属离子复合盐在恒温恒湿的25℃、RH95％±1％条件下放置10天吸潮增重量均低于5％，并具有相对稳定性，符合饲料添加剂对湿度的要求。
表2 N,N-二甲基甘氨酸有机酸多价金属离子复合盐的高湿稳定性研究
化合物 第5天(％) 第10天(％)
样品1 79.86±0.94 80.69±0.59
样品2 49.09±1.14 52.44±0.48
样品3 38.40±0.22 41.83±0.35
样品5 3.54±0.39 3.59±0.28
样品6 61.72±0.41 60.58±0.21
样品7 63.86±0.17 64.83±0.23
样品8 2.95±0.22 3.25±0.12
样品9 2.11±0.04 2.75±0.32
样品10 2.84±0.23 3.01±0.11
样品11 2.41±0.07 2.81±0.10
样品12 3.03±0.23 3.54±0.08
样品13 2.26±0.09 2.76±0.23
样品14 2.56±0.11 2.81±0.06
三、饲用组合物制备方法
实施例1～10的N,N-二甲基甘氨酸有机酸多价金属离子复合盐分别与相应的辅料混合制备相应的混合型颗粒饲料添加剂。
1.材料
原料：实施例1～10的N,N-二甲基甘氨酸有机酸多价金属离子复合盐、N,N-二甲基甘氨酸钠；
载体：玉米淀粉；
粘合剂：1.3％羟丙基甲基纤维素水溶液。
2.产品配方
表3 N,N-二甲基甘氨酸有机酸多价金属离子复合盐的混合型颗粒饲料添加剂的配方
产品名称 原料/质量份 载体/质量份 粘合剂/质量份
对照品1 N,N-二甲基甘氨酸钠  20 80 35
产品1 N,N-二甲基甘氨酸苯甲酸钙  20 80 35
产品2 N,N-二甲基甘氨酸富马酸钙  20 80 35
产品3 N,N-二甲基甘氨酸十四酸钙  20 80 35
产品4 N,N-二甲基甘氨酸对甲苯磺酸钙  20 80 35
产品5 N,N-二甲基甘氨酸苯甲酸铜  20 80 35
产品6 N,N-二甲基甘氨酸苯甲酸锌  20 80 35
产品7 N,N-二甲基甘氨酸富马酸锌  20 80 35
产品8 N,N-二甲基甘氨酸富马酸铜  20 80 35
3.生产工艺
本发明涉及的混合型颗粒饲料添加剂的生产工艺以下结合图1进行说明。
原料供应：广州英赛特生物技术有限公司研发中心，经品控部检验为合格产品，纯度≥99％。
辅料采购：从合格供应商处采购辅料，辅料到厂后抽样，经检验合格方能入库，存放备用，此过程为关键控制点，必须严格把控辅料质量。
生产领料、称量：根据产品配方的比例，对原料和辅料依次称重和复核，对产生的废弃物(包装袋)统一存放、处理。
混合：将原料和辅料投入混合机组混合均匀，此步骤为关键控制点，必须严格控制混合时间，定期对混合均匀度进行验证。混合机配有脉冲除尘器减少粉尘。
制粒：将原料和辅料混合后的产品与1.3％羟丙基甲基纤维素水溶液按照100:35的质量比例投入制粒机内，启动混合及切刀运行3-5min，物料制粒好以后进入流化床进行干燥，30min后过16目筛网。
包装和检验：根据包装规格进行称重打包，存入成品仓，标识生产批次和检验状态等信息，每一生产批次至少抽检两份样品送化验室进行出厂检验和留样。检验合格后方能出厂。由此得到各混合型颗粒饲料添加剂。
生产设备清洗：每一批产品生产完毕，必须对生产区域进行清洁。当更换生产品种时，必须对生产设备进行载体运转除杂，防止交叉污染。
三、动物饲养试验
实验例A N,N-二甲基甘氨酸有机酸多价金属离子复合盐在肉鸡料中的应用效果
试验采用单因子随机设计，选择22日龄、平均体重153g、体重相近的三黄羽肉鸡1200只，随机分为10个处理组，每组6个重复，公母各半，每个重复20只三黄羽肉鸡。试验前对鸡舍及器具进行消毒。试验期在同一鸡舍同一饲养管理条件下进行进行笼养。基础日粮以玉米-豆粕为主，整个饲养过程不额外添加其它抗氧化成分及促生长剂。各试验组分别为空白组、对照组、试验1～8组。其中空白组仅给与基础日粮，对照组和试验1～8组分别在基础日粮中添加5000ppm的本发明提供的混合型颗粒饲料添加剂产品(参见“饲用组合物的制备方法”部分)。试验期共20天，试验鸡自由饮水和采食，日喂料2次。以每个重复为单位，于42日龄称重(停料12h、不停水)，统计试验鸡耗料量，计算各组试验鸡的平均日采食量(ADFI)、平均日增重(ADG)和料肉比(FCR)。试验数据采用SPSS18软件进行统计分析，先对数据作单因素方差分析(ANOVA)，若处理间差异显著，再用Duncan's法进行多重比较，显著性水平为0.05。试验结果以“平均值±标准误”表示，试验结果如表4所示。从结果可知，与空白 组相比，对照组给与的供试品对试验鸡的采食量、平均日增重和料肉比具有显著的改善效果；试验组1～8与空白对照组相比，供试品对试验鸡的采食量影响不显著，但是平均日增重得到显著的提高的同时料肉比显著的下降；试验组1-8与对照组的试验结果相比，试验组1-4的料肉比改善不显著而试验组6-8的料肉比却显著的下降。
结论：在肉鸡的养殖实验中提高饲料的转化效率方面，本发明提供的N,N-二甲基甘氨酸苯甲酸钙、N,N-二甲基甘氨酸富马酸钙、N,N-二甲基甘氨酸十四酸钙和N,N-二甲基甘氨酸对甲苯磺酸钙具有与N,N-二甲基甘氨酸钠盐等效的养殖效果，而本发明提供的N,N-二甲基甘氨酸苯甲酸铜、N,N-二甲基甘氨酸苯甲酸锌、N,N-二甲基甘氨酸富马酸铜和N,N-二甲基甘氨酸富马酸锌比N,N-二甲基甘氨酸钠盐具有更优的养殖效果，与不给予任何饲料添加剂的实验组相比料肉比下降了约11％。
表4 N,N-二甲基甘氨酸有机酸多价金属离子复合盐对肉鸡生产性能影响结果
Figure PCTCN2017107673-appb-000011
实施例B N,N-二甲基甘氨酸有机酸多价金属离子复合盐在猪料中的应用研究
体重相近的65日龄杜长大三元杂瘦肉型小猪270头，随机分成9个处理组，每组3个重复，公母各半，每组10头。试验前对猪圈及器具进行消毒。试验期在同一猪圈同一饲养管理条件下分栏圈养。试验期间，以试验猪自由采食和饮水，日喂料2次。各试验组分别为对照组和试验1～10组。其中，对照组仅给与基础日粮，试验1～8组分别给予分别在基础日粮中添加1150ppm的本发明提供的混合型颗粒饲料添加剂产品1～13。整个饲养过程各试验组不额外添加其它抗氧化成分及促生长剂。试验周期28天，以每个重复为单位，统计试验猪的生产性 能，分别为平均日采食量(ADFI)、平均日增重(ADG)和料肉比(FCR)。试验数据采用SPSS18软件进行统计分析，先对数据作单因素方差分析(ANOVA)，若处理间差异显著，再用Duncan's法进行多重比较，显著性水平为0.05。试验结果以“平均值±标准误”表示，试验结果如表5所示。从结果可知，给与含有N,N-二甲基甘氨酸有机酸多价金属离子复合盐的试验组与对照组相比，试验猪的采食量没有受到显著影响，但是平均日增重显著的提高的同时料肉比下降了7.0％～12.5％。
表5 N,N-二甲基甘氨酸有机酸多价金属离子复合盐对小猪的生产性能影响
  供试品 试验数量 ADFI(kg) ADG(kg) FCR
对照组 - 10*3 11.87±0.32 4.51±0.08a 2.63±0.02a
试验1组 产品1 10*3 12.73±0.33 5.26±0.10b 2.42±0.02b
试验2组 产品2 10*3 12.40±0.26 5.13±0.07b 2.42±0.02b
试验3组 产品3 10*3 12.77±0.20 5.22±0.10b 2.44±0.01b
试验4组 产品4 10*3 12.53±0.32 5.17±0.14b 2.43±0.01b
试验5组 产品5 10*3 12.53±0.27 5.44±0.12b 2.30±0.01e
试验6组 产品6 10*3 12.43±0.43 5.27±0.21b 2.37±0.01c
试验7组 产品7 10*3 12.50±0.38 5.31±0.18b 2.36±0.01cd
试验8组 产品8 10*3 12.70±0.26 5.49±0.13b 2.31±0.01de
实施例C N,N-二甲基甘氨酸有机酸多价金属离子复合盐在水产料中的应用
(1)试验材料
试验用鱼：所用试验鱼为草鱼，当年鱼种，由广东省惠州市大丰鱼种场。健康活泼、规格一致的草鱼种在大网箱中(4×2×1.5m3)饲养4周后才用于正式养殖试验，实验体系为浮性小网箱(规格1.1×1.1×1.1m3)，每个小网箱均置有一个充气头，每天24h充气。小网箱与暂养网箱均置于试验场一个3500m2的池塘中，池塘水深约1.5m，池塘水为充分曝气底下水。试验时，将饥饿1天的草鱼432尾随机分成9组，每组设4个重复，每个重复放12尾鱼，以每个重复为单位称重后放入36个网箱中，分别饲喂不同的试验饲料。
试验饲料：试验用饲料按表6配方自行配制，不同试验组按表7分别加入相同剂量的不同的N,N-二甲基甘氨酸有机酸多价金属离子复合盐。所用饲料原料经超微粉碎后通过江苏牧羊膨化机组制成粒径3mm浮性膨化饲料，出模温度130℃，通过喷油设备外喷3％豆油，阴凉处密封保存备用。
表6 试验用草鱼饲料配方及化学成分(％wt.)
原料组成 含量(％) 原料组成 含量(％)
鱼粉 9.0 豆油 3.0
肠衣粉 3.0 磷脂菜粕 9.0
豆粕 12.0 谷朊粉 4.0
菜粕 12.0 血球粉 2.0
味精蛋白 3.0 Vc-磷酸酯 0.1
次粉 12.6 磷酸二氢钙 1.8
面粉 17.0 氯化胆碱 0.2
膨润土 0.70 多维 0.1
米糠 10.0 微矿预混剂 0.5
表7 N,N-二甲基甘氨酸有机酸多价金属离子复合盐的促生长试验分组
组别 供试品 剂量(ppm)
空白对照组 - -
试验1组 N,N-二甲基甘氨酸苯甲酸钙 450
试验2组 N,N-二甲基甘氨酸富马酸钙 450
试验3组 N,N-二甲基甘氨酸十四酸钙 450
试验4组 N,N-二甲基甘氨酸对甲苯磺酸钙 450
试验5组 N,N-二甲基甘氨酸苯甲酸铜 450
试验6组 N,N-二甲基甘氨酸苯甲酸锌 450
试验7组 N,N-二甲基甘氨酸富马酸锌 450
试验8组 N,N-二甲基甘氨酸富马酸铜 450
(2)试验方法
试验管理：试验采用人工限食投喂，投食量每周调整一次，每组投喂水平(按初始体重)完全一致，每天投喂两次(7:30及15:00)。试验为期8周。试验期间定时对水质进行监控，养殖全程水温26.88±3.08℃、DO>5.0mg O L-1、pH 7.8、氨氮<0.50mg N L-1、亚硝酸盐氮<0.05mg N L-1。
参数统计：试验时，停喂1d后对各网箱鱼进行整体称重，计算其增重率(WG,％)、饲料系数(FCR)和存活率(SR,％)。计算公式如下：
增重率(WG，％)＝100×(平均末重－平均初重)/平均初重；
饲料系数(FCR)＝摄食量/鱼体增重；
存活率(SR，％)＝100×试验结束时鱼数量/试验开始时鱼数量。
(3)试验结果
N,N-二甲基甘氨酸有机酸多价金属离子复合盐对草鱼的生产性能的影响结果见表8。结果显示添加了N,N-二甲基甘氨酸有机酸多价金属离子复合盐的试验组在增重和饲料系数方面均优于空白对照组，具有明显的促生长效应，另外，还可显著提高草鱼的存活率，具有明显的改善草鱼的抗缺氧能力。
表8 N,N-二甲基甘氨酸有机酸多价金属离子复合盐在水产料中的应用试验结果
  初重(g) 末重(g) 增重率(％) (FCR) SR(％)
空白对照组 251.25±4.09 585.55±11.53 133.15±4.54 1.50±0.05 56.25±9.24a
试验1组 253.25±4.19 596.47±13.08 135.48±2.16 1.46±0.04 85.42±3.99b
试验2组 254.25±3.64 598.31±5.61 135.48±4.28 1.46±0.06 89.58±3.99b
试验3组 250.50±3.38 598.90±9.16 139.15±3.65 1.44±0.03 75.00±7.61b
试验4组 252.50±2.84 602.98±4.17 138.90±3.17 1.43±0.02 81.25±7.11b
试验5组 256.25±2.01 608.72±5.87 137.60±3.16 1.42±0.03 79.17±5.38b
试验6组 253.00±1.78 604.66±10.81 138.96±3.28 1.43±0.04 79.16±8.67b
试验7组 253.25±2.29 607.01±6.05 139.76±3.47 1.42±0.03 93.75±3.99b
试验8组 255.25±1.31 608.50±9.48 138.44±4.43 1.42±0.04 95.83±2.40b
实施例D N,N-二甲基甘氨酸富马酸锌在断奶猪料中的应用研究
体重相近的杜长大三元杂瘦肉型断奶仔猪240头，随机分成8个处理组，每组3个重复，公母各半，每组10头。试验前对猪圈及器具进行消毒。试验期在同一猪圈同一饲养管理条件下分栏圈养。试验期间，以试验猪自由采食和饮水，日喂料3次。各试验组分别为对照组、对比例和试验1～6组。其中，对照组仅给与基础日粮，对比例给与2500ppm的氧化锌、试验1～6组分别给予分别在基础日粮中添加不同剂量的本发明提供的混合型颗粒饲料添加剂产品7，见表9。整个饲养过程各试验组不额外添加其它抗氧化成分及促生长剂。试验周期15天，以每个重复为单位，统计试验猪的生产性能，分别为平均日采食量(ADFI)、平均日增重(ADG)和料肉比(FCR)。试验数据采用SPSS18软件进行统计分析，先对数据作单因素方差分析(ANOVA)，若处理间差异显著，再用Duncan's法进行多重比较，显著性水平为0.05。试验结果以“平均值±标准误”表示，试验结果如表9所示。从结果可知，N,N-二甲基甘氨酸富马酸 锌对断奶猪的采食量影响不显著；对平均日增重的影响呈现一定的剂量效应，当剂量达到260ppm左右可显著的提高断奶猪的平均日增重并达到2500ppm氧化锌的水平；可降低料肉比但是剂量高于390ppm时才具有显著性并达到高剂量氧化锌的水平。
表9 N,N-二甲基甘氨酸富马酸锌对断奶猪的生产性能影响
Figure PCTCN2017107673-appb-000012
实验例E N,N-二甲基甘氨酸富马酸铜在断奶猪中的应用效果
体重相近的杜长大三元杂瘦肉型断奶仔猪180头，随机分成6个处理组，每组3个重复，公母各半，每组10头。试验前对猪圈及器具进行消毒。试验期在同一猪圈同一饲养管理条件下分栏圈养。试验期间，以试验猪自由采食和饮水，日喂料3次。各试验组分别为对照组、对比例和试验1～6组。其中，对照组仅给与基础日粮，对比例给与250ppm的五水硫酸铜、试验1～4组分别给予分别在基础日粮中添加不同剂量的本发明提供的混合型颗粒饲料添加剂产品8，见表10。整个饲养过程各试验组不额外添加其它抗氧化成分及促生长剂。试验周期15天，以每个重复为单位，统计试验猪的生产性能，分别为平均日采食量(ADFI)、平均日增重(ADG)和料肉比(FCR)。试验数据采用SPSS18软件进行统计分析，先对数据作单因素方差分析(ANOVA)，若处理间差异显著，再用Duncan's法进行多重比较，显著性水平为0.05。试验结果以“平均值±标准误”表示，试验结果如表10所示。从结果可知，N,N-二甲基甘氨酸富马酸铜对断奶猪的采食量和平均日增重没有显著的影响，但是在使用剂量为30-100ppm时就可显著的降低料肉比的水平，当使用剂量达到100ppm时料肉比的下降水平相比对照组下降了8.61％，与高剂量五水硫酸铜的作用水平相当。
表10 N,N-二甲基甘氨酸富马酸铜对断奶猪的生产性能影响
Figure PCTCN2017107673-appb-000013
以上所述实施例仅表达了本发明的几种实施方式，还有其他方式用来实施本发明。相应地，本发明的实施例是将作为例证进行说明，但并不能因此而理解为对本发明的专利范围的限制，还可能是在本发明范围内以及同一发明构思内所作的修改或在权利要求中所添加的等同内容。

Claims (12)

  1. 一种N,N-二甲基甘氨酸有机酸多价金属离子复合盐，包含N,N-二甲基甘氨酸根离子、与所述N,N-二甲基甘氨酸根离子相等摩尔量的多价金属离子和与所述N,N-二甲基甘氨酸根离子及所述多价金属离子等化学当量的饲料可接受的有机酸根离子。
  2. 根据权利要求1所述的N,N-二甲基甘氨酸有机酸多价金属复合盐，其特征在于，所述的多价金属离子为二价金属离子。
  3. 根据权利要求2所述的N,N-二甲基甘氨酸有机酸多价金属复合盐，其特征在于，所述的二价金属离子为Ca(II)、Mg(II)、Cu(II)、Zn(II)、Fe(II)、Mn(II)、Co(II)或Ni(II)。
  4. 根据权利要求1所述的N,N-二甲基甘氨酸有机酸多价金属复合盐，其特征在于，所述的有机酸根离子对应的有机酸为苯甲酸、对甲苯甲酸或富马酸。
  5. 根据权利要求1-4任一项所述的N,N-二甲基甘氨酸有机酸多价金属离子复合盐，其特征在于，选自：
    I.包含N,N-二甲基甘氨酸根离子、与所述N,N-二甲基甘氨酸根离子相等摩尔量的Ca(II)和与所述N,N-二甲基甘氨酸根离子及所述Ca(II)等化学当量的苯甲酸根离子的N,N-二甲基甘氨酸有机酸多价金属离子复合盐；
    II.包含N,N-二甲基甘氨酸根离子、与所述N,N-二甲基甘氨酸根离子相等摩尔量的Ca(II)和与所述N,N-二甲基甘氨酸根离子及所述Ca(II)等化学当量的富马酸根离子的N,N-二甲基甘氨酸有机酸多价金属离子复合盐；
    III.包含N,N-二甲基甘氨酸根离子、与所述N,N-二甲基甘氨酸根离子相等摩尔量的Cu(II)和与所述N,N-二甲基甘氨酸根离子及所述Cu(II)等化学当量的苯甲酸根离子的N,N-二甲基甘氨酸有机酸多价金属离子复合盐；
    IV.包含N,N-二甲基甘氨酸根离子、与所述N,N-二甲基甘氨酸根离子相等摩尔量的Cu(II)和与所述N,N-二甲基甘氨酸根离子及所述Cu(II)等化学当量的富马酸根离子的N,N-二甲基甘氨酸有机酸多价金属离子复合盐；
    V.包含N,N-二甲基甘氨酸根离子、与所述N,N-二甲基甘氨酸根离子相等摩尔量的Zn(II)和与所述N,N-二甲基甘氨酸根离子及所述Zn(II)等化学当量的苯甲酸根离子的N,N-二甲基甘氨酸有机酸多价金属离子复合盐；
    VI.包含N,N-二甲基甘氨酸根离子、与所述N,N-二甲基甘氨酸根离子相等摩尔量的Zn(II)和与所述N,N-二甲基甘氨酸根离子及所述Zn(II)等化学当量的富马酸根离子的N,N-二甲 基甘氨酸有机酸多价金属离子复合盐。
  6. 一种饲用组合物，包含权利要求1-5任一项所述的N,N-二甲基甘氨酸有机酸多价金属离子复合盐或其溶剂合物的至少一种和可饲用辅料。
  7. 根据权利要求6所述的饲用组合物，其特征在于，还包含附加的动物饲料添加剂，所述的附加的动物饲料添加剂选自营养性饲料添加剂、一般饲料添加剂或药物饲料添加剂。
  8. 根据权利要求6或权利要求7所述的饲用组合物，其特征在于，还包含饲料原料。
  9. 权利要求1-5任一项所述的N,N-二甲基甘氨酸有机酸多价金属离子复合盐或其溶剂合物在制备动物饲料添加剂中的应用。
  10. 权利要求1-5任一项所述的N,N-二甲基甘氨酸有机酸多价金属离子复合盐或其溶剂合物在制备动物饲料中的应用。
  11. 权利要求6-8任一项所述的饲用组合物在制备动物饲料添加剂中的应用。
  12. 权利要求6-8任一项所述的饲用组合物在制备动物饲料中的应用。
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