CN101981000A - Method for the continuous synthesis of an N-acylated compound, and equipment for implementing said method - Google Patents
Method for the continuous synthesis of an N-acylated compound, and equipment for implementing said method Download PDFInfo
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- CN101981000A CN101981000A CN200980111317XA CN200980111317A CN101981000A CN 101981000 A CN101981000 A CN 101981000A CN 200980111317X A CN200980111317X A CN 200980111317XA CN 200980111317 A CN200980111317 A CN 200980111317A CN 101981000 A CN101981000 A CN 101981000A
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- C07C233/45—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups
- C07C233/46—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
- C07C233/47—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of an acyclic saturated carbon skeleton
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- C07C233/46—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
- C07C233/49—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a carbon atom of an acyclic unsaturated carbon skeleton
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Abstract
The invention relates to the continuous aqueous-phase synthesis of an N-acylated compound including a unit (M1) of the formula (I) in which n is 0, 1 or 2 and R1 is an aliphatic radical, wherein said synthesis comprises: the step A of reacting a compound including a unit (M2) of the formula (II), in which M is an alkaline metal atom, with a halide acid of the formula (IV): formula (III) in which X is a halogen atom, in an aqueous solution and at a pH higher than 7 in order to form a N-acylated compound including a unit (M3) of the formula (IV); the step B of hydrolysing, at a pH lower than 7, the N-acylated compound including at least one unit (M3) and obtained during the step A, in order to form the N-acylated compound including a unit (M1); characterised in that the step A is carried out by continuously contacting in time a flow at a flow rate d1 of said halide acid of the formula (IV), a flow at a flow rate d2 of said compound including at least one unit (M2) or a mixture of compounds including at least one unit (M2), and a flow at a flow rate d3 of the alkaline aqueous solution, while maintaining the molar ratio between the acid halide of the formula (IV) and the compound including at least one unit (M2) lower than 1 and higher than or equal to 0.75, and while maintaining the pH of the medium lower than or equal to 9.5 and higher than or equal to 8. The invention also relates to equipment for implementing said method.
Description
The present invention relates to amino acid whose acidylate and the gained acylate purposes in preparation makeup and pharmaceutical composition.
Known amine functional group is called Xiao Te-Bao Man (Schotten-Baumann) reaction above a century by the acylation reaction of chloride of acid; It is widely used in N-acyl derivative, the N-acyl derivative of protein hydrolysate partially or completely of preparation a-amino acid.This purposes for example is disclosed in U.S. Pat 2,463,779 and the international application published with number WO 92/21318 and WO 94/26694 in.
Conventional process for acylating comprises the salifiable preliminary step of amino acid, is thereafter with the step of chloride of acid with amino acid whose salt acidylate, is the step with gained N-acyl group salt hydrolysis then.
Yet, in this method, acylation reaction and following side reaction competition, this produces the lipid acid homologue of chloride of acid in undesired mode:
R1-C(＝O)-Cl+NaOH----------＞R1-C(＝O)-H+NaCl。
Latter's side reaction limits by chloride of acid or chloride of acid and amino acid whose mixture are dissolved in organic solvent such as acetone or the methyl ethyl ketone, to prevent and the development that is present in the sodium hydroxide side reaction of aqueous phase.Yet acetone is the potential dangerous solvents, and it is very thorny that this makes this method get up.In addition, this method is carried out with batch mode with the batch of material of 700kg final product, and this need use about 0.5m
3Reactor and the solvent of significant quantity.
With number US 5; 942,635 U.S. Patent Publications of publishing a kind of by making the materials flow of the sodium sarcosinate aqueous solution, oleoyl chloride materials flow and methyl ethyl ketone materials flow circulation simultaneously and keep the method for pH synthetic continuously N-acyl amino carboxylic acid or sulfonic acid by adding sodium hydroxide solution simultaneously in tubular reactor more than or equal to 10.
Von Marian etc. (Tenside Detergents, 17 (1980), 4, the 174-176 page or leaf) disclose the continuation method of aminocarboxylic acid or sulfonic acid acidylate in the special reaction device, and this causes the by product of the lipid acid of Synthetic 2-4 weight % as reaction.
US 2,463, and 779 described another programs are that the existence of considering side reaction uses excessive chloride of acid, and 1-1.5 mole chloride of acid/mole amine functional group is to guarantee the acidylate of all amine functional groups.Because it unnecessarily consumes chloride of acid and produces unwanted lipid acid, therefore this scheme is not satisfied.
Here it is why in the context of its research, be intended to make existing method to the method development of littler danger and the equipment of use reduced size, satisfy the quality standard of final product aspect the amount of residual fat acid simultaneously, the inventor has developed and has been the method for present patent application theme.
According to first aspect, theme of the present invention is in the synthetic method of mixture that comprises at least one divalence functional unit's (M1) N-acyl compounds or comprise at least one divalence functional unit's (M1) N-acyl compounds of aqueous phase:
Wherein n represents to equal 0,1 or 2 integer, and R1 represents to comprise the saturated or undersaturated linearity or the branched aliphatic group of 1-17 carbon atom, and described method comprises:
Steps A: make the compound that comprises at least one divalence functional unit (M2) or comprise the mixture of at least one divalence functional unit's (M2) compound:
Wherein n aforementioned definition in the divalence functional unit (M1), M represents alkali metal atom, and formula (IV) acyl halide:
R1 aforementioned definition the among the divalence functional unit (M1) as described wherein; X represents the atom from halogen, or with the mixture of formula (IV) acyl halide in the aqueous solution and comprise at least one divalence functional unit's (M3) N-acyl compounds with formation greater than reaction under 7 the pH:
Wherein n, M and R1 or comprise the mixture of at least one divalence functional unit's (M3) N-acyl compounds as defined above;
Step B: N-acyl compounds that comprises at least one divalence functional unit (M3) that under less than 7 pH, obtains in steps A or the mixture hydrolysis that comprises at least one divalence functional unit's (M3) N-acyl compounds, to form described N-acyl compounds or the described mixture that comprises at least one divalence functional unit's (M1) N-acyl compounds that comprises at least one divalence functional unit (M1);
It is characterized in that: steps A is following carries out: making flow velocity is d
1The materials flow of described formula (IV) acyl halide, flow velocity be d
2Described mixture stream and the flow velocity that comprises at least one divalence functional unit's (M2) compound or comprise at least one divalence functional unit's (M2) compound be d
3Alkaline aqueous solution materials flow Continuous Contact As time goes on; while freeze mode (IV) acyl halide/comprise at least one divalence functional unit's (M2) compound mol ratio less than 1 and more than or equal to 0.75; keep the pH of medium to be less than or equal to 9.5 simultaneously, more particularly be less than or equal to 9 and more than or equal to 8.In the method for above definition, statement " from the atom of halogen " is X, chlorine atom or the bromine atoms in the expression (IV) in principle.
In the method for above definition, aqueous sodium hydroxide solution or potassium hydroxide aqueous solution are represented in statement " alkaline aqueous solution " in principle.
M, sodium or the potassium among divalence functional unit M2 and the M3 is represented in statement " basic metal " in principle.
As the method for previous definition in, formula (IV) acyl halide is illustrated under the barometric point being less than or equal to and is any acyl halide of liquid under 40 ℃ the temperature:
Statement " the saturated or undersaturated linearity or the branched aliphatic group that comprise 1-17 carbon atom " expression is more particularly for R1 and divalence functional unit M1 and M3 in the formula (IV), the linearity or branched-alkyl or linearity or the branched chain thiazolinyl that comprise 5-13 carbon atom more particularly also have amyl group, hexyl, heptyl, octyl group, nonyl, decene base, decyl or undecyl.
In the method for above definition, statement " the N-acyl compounds that comprises at least one divalence functional unit (M2) " is represented in principle:
The part N-acyl group protein hydrolysate in-any source, it is mainly by being less than or equal to 10 by basic solution such as sodium hydroxide or the oligomeric degree of potassium hydroxide aqueous solution neutral, and the mixture that more particularly is less than or equal to 5 oligopeptide is formed;
The complete N-acyl group protein hydrolysate in-any source, it is mainly by being less than or equal to 2 by basic solution such as sodium hydroxide or potassium hydroxide aqueous solution neutral amino acid and oligomeric degree, and the mixture that more particularly is less than or equal to 1.5 oligopeptide is formed;
-an alkali metal salt, amino acid more especially, be mainly the sodium salt or the sylvite of the a-amino acid of natural origin, or derivatives thereof, the more especially an alkali metal salt of Padil, L-Ala, Serine, aspartic acid, L-glutamic acid, Xie Ansuan, Threonine, arginine, Methionin, proline(Pro), leucine, phenylalanine, Isoleucine, Histidine, tyrosine, tryptophane, l-asparagine, glutamine, halfcystine, Gelucystine, methionine(Met), oxyproline, hydroxylysine, sarkosine, ornithine, 2-aminoisobutyric acid; Or an alkali metal salt of beta-amino acids such as Beta-alanine; Or an alkali metal salt of gamma-amino acid such as γ-An Jidingsuan.
Therefrom obtain these protein as the partially or completely hydrolysate in the method for previous definition, can be animal-origin, osso-albumin for example, elastin, fish protein, isinglass, Keratin sulfate or casein, plant origin, cereal plants for example, the protein of flower or fruit, for example soybean, Sunflower Receptacle, oat, wheat, corn, barley, peanut, Chinese sorghum, rice, buckwheat, rye, potato, Radix Dauci Sativae, tomato, lupine, broad bean, Sweet Apricot seed, Kiwifruit, mango, banana, coconut, palm-kernel, orange, plum, Fructus Vins, the protein that pears or apple produce; They also can be the protein that is obtained by green alga (unicellular algae), powder algae (pink algea), yeast or silk.
Hydrolysate for example obtains by the protein heating that will be placed under 60-130 ℃ temperature in acid or the alkaline medium.
The also available proteolytic enzyme enzyme catalysis of this hydrolysis is carried out, optional and alkaline or acid posthydrolysis associating.During the proteinic aminogram of some plant origins is listed in the table below:
Table A
Table A (continuing)
According to a concrete aspect of the method for above definition, steps A is carried out with the mixture of formula (IV) compound, and wherein R1 represents to comprise the alkyl of 7-11 carbon atom.According to this concrete aspect, the mixture of formula (IV) compound is the mixture by the chloride of acid of the mixture preparation of the lipid acid of Oleum Cocois generation.
According to as another concrete aspect of the method for previous definition, by the pH of control reaction medium with it comes the carrying out of the chemical reaction of monitoring step A by adding the alkaline aqueous solution adjusting if necessary.
According to another concrete aspect as the previous method that defines, carry out steps A, keep temperature less than 35 ℃ simultaneously.
As the method for previous definition in, the steps A of method is preferably carried out with contacting between the compound that promotes to comprise divalence functional unit (M2) and formula (IV) acyl halide along with brute force stirs.
According to another the concrete aspect as the previous method that defines, steps A is undertaken by contacting with the compound that comprises divalence functional unit (M2) at duration freeze mode (IV) acyl halide that is less than or equal to 5 minutes.
As the method for previous definition in, the step B of method preferably uses strong acid, along with stirring is carried out, with contacting between the compound that promotes to comprise divalence functional unit (M3) and the aqueous acid.Strong acid more particularly is selected from hydrochloric acid, sulfuric acid or phosphoric acid.
According to another concrete aspect as the previous method that defines, carry out step B, keep pH to be less than or equal to 2 simultaneously.
According to as another concrete aspect of the method for previous definition, behind the step B for wash with water with filtration step B in the step C of gained throw out dispersion.
According to another concrete aspect, behind the step C the sedimentary step D of gained among the drying step C as the previous method that defines.
According to one of method as defined above aspect more specifically, with gained drying precipitate and spraying drying among the step C to obtain powder.
According to another concrete aspect of the present invention, a theme of the present invention is synthesis type (I) N-acyl alpha-amino acid whose method as defined above:
R1 aforementioned definition the among the divalence functional unit (M1) as described wherein, R2 represents hydrogen atom, or is selected from the group of methyl, benzyl, isobutyl-, 1-methyl-propyl or sec.-propyl, and R3 represents hydrogen atom or methyl, described method comprises:
Steps A: an alkali metal salt that makes the a-amino acid of formula (II):
Wherein R2 and R3 define in the formula (I) and M represents alkali metal atom as described above, and formula (IV) acyl halide:
Wherein R1 represents to comprise the saturated or undersaturated linearity or the branched aliphatic group of 1-17 carbon atom, and X represents halogen atom, or with the mixture of formula (IV) acyl halide, in the aqueous solution and under, react greater than 7 pH, to form formula (III) compound:
Wherein M, R1, R2 and R3 as defined above, or the mixture of formula (III) compound;
Step B: under less than 7 pH with steps A in the mixture hydrolysis of gained formula (III) compound or formula (III) compound, to form described formula (I) N-acyl group a-amino acid;
It is characterized in that: steps A is following carries out: making flow velocity is d
1Described formula (IV) acyl halide materials flow and flow velocity be d
2Described formula (II) a-amino acid materials flow and flow velocity be d
3Alkaline aqueous solution materials flow Continuous Contact As time goes on, freeze mode (IV) acyl halide/formula (II) a-amino acid mol ratio is below 1 simultaneously.
According to a concrete aspect of method as defined above, in formula (IV), X represents the chlorine atom.
According to a concrete aspect of method as defined above, in formula (IV), and with regard to divalence functional unit M1 and M3, R1 represents heptyl.
According to another concrete aspect of the present invention, a method that themes as synthesis type as defined above (I ') N-capryloyl Padil of the present invention:
Represent heptyl corresponding to R1 wherein, R2 and R3 represent the formula (I) of hydrogen atom separately, and described method comprises:
Steps A: make formula (II ') Sodium Glycinate:
Represent the formula (II) of sodium atom corresponding to M wherein, and capryl(yl)chloride (IV '):
Represent that corresponding to R1 wherein heptyl and X represent the formula (IV) of chlorine atom, in aqueous sodium hydroxide solution and greater than 8 and be less than or equal under 9.5 the pH and react, to form formula (III ') compound:
Represent heptyl corresponding to R1 wherein, M represents sodium atom, and R1 represents that heptyl and R2 and R3 represent the formula of hydrogen atom (III) separately;
Step B: under less than 2 pH with steps A in gained formula (III ') compound hydrolysis, to form described formula (I ') N-capryloyl Padil;
Step C: wash with water and filtration step B in the sedimentary water dispersion of gained; With
Step D: with the moist precipitate thing drying/spraying drying that obtains among the step C, to obtain the N-capryloyl Padil of fine powder form;
It is characterized in that: steps A is following carries out: making flow velocity is d
1Described formula (IV ') acyl halide materials flow and flow velocity be d
2Described formula (II ') a-amino acid materials flow and flow velocity be d
3Aqueous sodium hydroxide solution materials flow Continuous Contact As time goes on, freeze mode (IV) acyl halide/formula (II ') a-amino acid mol ratio is less than 1 and more than or equal to 0.8 simultaneously.
According to another concrete aspect of method as defined above, in formula (IV) and with regard to divalence functional unit M1 and M3, R1 represents 9-decene base.
According to another concrete aspect of the present invention, a theme of the present invention is the method as the continuous N-of the preparation acylamino acid of previous definition, it is characterized in that being d with more than or equal to 0.8 and less than chloride of acid/amino acid molar ratio of 1 with flow velocity
2Amino acid solution, flow velocity be d
1Chloride of acid and flow velocity be d
3Aqueous sodium hydroxide solution introduce simultaneously in the reactor that is equipped with agitator, the feasible meticulous homogenizing that can obtain described reaction medium of described reactor, and its size makes the residence time of reaction medium in reactor that forms be less than or equal to 5 minutes, wherein described reaction medium is remained under the temperature that is less than or equal to 35 ℃, and the pH of described reaction medium is remained under the value of 8.5-9.5; Wherein make described reaction medium be transferred to the precipitation reactor that is equipped with worm screw, therein in order to flow velocity d
4The phosphate aqueous solution of introducing is handled described reaction medium, make and in described precipitation reactor, can keep being less than or equal to 2 pH, to form the sedimentary water dispersion of described amino acid at the end that flows through described precipitation reactor, then with its washing and filtration, if necessary with gained moist precipitate thing drying, spraying drying then.
According on the other hand, one of the present invention themes as the equipment that carries out as the method for previous definition, and it comprises:
Be equipped with agitator (AG1) and be used to measure the jacketed reactor (RE1) of the device (TICRE1) of internal temperature, it can circulate in described chuck by refrigerant and control and regulate wherein temperature, and wherein said refrigerant cools off by recirculation in interchanger (E1);
Three container ZB1, ZB2 and ZB3 will comprise at least one divalence functional unit (M2), formula (IV) acyl halide and alkaline aqueous solution respectively continuously from wherein discharging by 3 pumps (P1), (P2) with (P3) respectively;
Three liquid flow lines (1), (2) and (3), it can make reactant flow out from described container (ZB1), (ZB2) with (ZB3) and introduce described reactors (RE1) by 3 inlets that are arranged in reactor (RE1) bottom;
Be equipped with the precipitation reactor (PR1) of worm screw (AG2), it is connected on the inlet that is positioned at described reactor (RE1) top by liquid flow line (4), and be connected on the container (ZB4) by liquid flow line (5), to be intended to the acidic aqueous solution that in described precipitation reactor (PR1) hydrolysis comprises at least one divalence functional unit's (M3) compound by pump (P4) discharges from container (ZB4), wherein said precipitation reactor (PR1) adds cover with chuck in its first half part that is called that upstream half divides, described chuck can circulate in described chuck by refrigerant and control and regulate wherein temperature, add cover by chuck in its second half part that is called that downstream half divides, described chuck can circulate in described chuck by heating fluid and control and regulate wherein temperature;
That can reclaim from described precipitation reactor (PR1) effusive throw out dispersion holds groove (R02), it is equipped with pH control device (PHR02), its in its tract by liquid flow line (6), (7) and (8) be connected the set filter (F1) that is arranged in parallel, (F2) and (F3) on, described strainer by pump (P5) with being connected of waterworks, can wash and filter by described and hold the throw out dispersion that groove (R02) produces; Described strainer (F1), (F2), (F3) are connected in the downstream and rise in the described groove that holds (on the liquid flow line (9) of the overflow of R02.
According to last aspect of the present invention; a following compound that themes as to obtain of the present invention by above-mentioned define method in topical cosmetic composition as activeconstituents and/or as the purposes of vehicle: the part N-acyl group protein hydrolysate in any source; it is mainly by being less than or equal to 10 by alkali metal base such as sodium hydroxide or the oligomeric degree of potassium hydroxide aqueous solution neutral; the mixture that more particularly is less than or equal to 5 oligopeptide is formed; the complete N-acyl group protein hydrolysate in any source; it is mainly by being less than or equal to 2 by alkali metal base such as sodium hydroxide or potassium hydroxide aqueous solution neutral amino acid and oligomeric degree; the mixture that more particularly is less than or equal to 1.5 oligopeptide is formed; N-acyl alpha-amino acids; N-acyl amino acetate more particularly; N-acyl group L-Ala; N-acyl group Serine; the N-acylaspartic acid; the N-acyl glutamic acid; N-acyl group Xie Ansuan; N-acyl group Threonine; N-acyl group arginine; the N-acyl-lysine; N-acyl group proline(Pro); N-acyl group leucine; N-acyl group phenylalanine, N-acyl group Isoleucine, N-acyl group Histidine; N-acyl group tyrosine; N-acyl group tryptophane, N-acyl group l-asparagine, N-acylaminoglutaricamiderivative; N-acyl group halfcystine; N-acyl group Gelucystine, N-acyl group methionine(Met), N-acyl group oxyproline; N-acyl group hydroxylysine; N-acyl group ornithine, N-acyl group alpha-amino acid derivatives, more particularly N-acyl group sarkosine.
The topical cosmetic composition that comprises the complete N-acyl group protein hydrolysate that the N-acyl group protein hydrolysate in any source and/or the method by previous definition obtain is usually with moisture or the aqueous alcohol of dilution or the form of aqueous ethanol solution; with simple or multiple emulsion; for example the form of water-in-oil (W/O), oil-in-water (O/W), water-in-oil-in-water (W/O/W) or water-in-oil bag oil (O/W/O) emulsion exists, and wherein oil is plant or mineral or animal-origin.They also can disperse or immerse in fabric or the nonwoven cloth material, and no matter they are handkerchief, paper handkerchief or clothes.
Usually; by the N-acyl group protein hydrolysate in any source and/or the complete N-acyl group protein hydrolysate and the multiclass auxiliary that is used for cosmetic formulations or active compound combined that obtains as the previous method that defines; no matter they are fatty substance; organic solvent; thickening material; jelling agent; negative catalyst; antioxidant; opalizer; stablizer; whipping agent; softener; spices; ion or nonionic emulsifying agent; filler; sequestering agent; sequestrant; sanitas; volatile oil; dyestuff; pigment; hydrophilic or lipotropy promoting agent; wetting Agent for Printing Inks such as glycerine; sanitas; cosmetic active agent; mineral and/or organic sunscreen agent; mineral filler such as ferriferous oxide; titanium oxide and talcum; synthetic filling such as crosslinked or non-crosslinked polymethylmethacrylate and nylon; silicone elastomer; sericite or plant milk extract; or lipid vesicle, or any routine is used for the composition of makeup.
Example as the oil of the complete N-acyl group protein hydrolysate associating that can obtain with the N-acyl group protein hydrolysate in any source and/or by subject methods of the present invention, can mention mineral oil, for example whiteruss, petrosio, isoparaffin or slab oil; The oil of animal-origin, for example squalene or squalane; Vegetables oil, for example sweet almond oil, Oleum Cocois, Viscotrol C, jojoba oil, sweet oil, rapeseed oil, peanut oil, sunflower oil, wheatgerm oil, Fructus Maydis oil, soya-bean oil, Oleum Gossypii semen, alfalfa oil (alfalfa oil), poppy seed oil, Semen Cucurbitae oil, Oenothera oil, grain oil, big wheat oil, rye-seed oil, Thistle oil, lumbang oil, passionflower oil, hazelnut oil, plam oil, shea butter, Prunus amygdalus oil, calophyllum inophyllum kernel oil, water garlic tori seed oil, Lipoval A or Flos Inulae oil; The ethoxylation vegetables oil; Synthetic oil, fatty acid ester for example, butyl myristate for example, propyl myristate, cetyl myristate, Wickenol 111, butyl stearate, the stearic acid cetyl ester, isopropyl stearate, octyl stearate, Standamul 7061, the oleic acid dodecyl ester, lauric acid hexyl ester, two sad propylene glycol esters, ester derived from lanolin fatty acid, the different cetyl of lanolin fatty acid isopropyl ester or lanolin fatty acid for example, fatty acid glycerine one ester, triglyceride and triglyceride level, triheptin for example, phenylformic acid alkyl ester, poly-(alpha-olefin) class, for example polyisobutene synthesizes different paraffinic, for example isohexadecane or Permethyl 99A., perfluorination oils and silicone oil.In the latter, can more particularly mention the polysiloxane of polysiloxane, lipid acid and the pure modification of the polysiloxane of polydimethylsiloxane, PSI, amine modification, fatty acid modified polysiloxane, pure modification, the polysiloxane of polyether group modification, the polysiloxane of epoxy group(ing) modification, polysiloxane, cyclic polysiloxanes and the alkyl-modified polysiloxane of fluorinated groups modification.
As other fatty substances of the complete N-acyl group protein hydrolysate associating that can obtain, can mention Fatty Alcohol(C12-C14 and C12-C18) or lipid acid with the N-acyl group protein hydrolysate in any source and/or by subject methods of the present invention.
Wherein, can for example be the homopolymer or the multipolymer of vinylformic acid or acrylic acid derivative with the N-acyl group protein hydrolysate in any source and/or by thickening and/or Emulgating polymers that the complete N-acyl group protein hydrolysate that subject methods of the present invention obtains is united; the homopolymer of methacrylic acid or methacrylic acid derivative or multipolymer; the homopolymer of acrylamide or multipolymer; the homopolymer of acrylamide derivative or multipolymer; the homopolymer of acrylamide group methyl propane sulfonic acid or multipolymer; the homopolymer of vinyl monomer or multipolymer; muriatic homopolymer of vinylformic acid trimethylammonium amino ethyl ester or multipolymer; the hydrocolloid in plant or biosynthesizing source; xanthan gum for example; kuteera gum; carragenates (carrageenate) or alginate; silicate; Mierocrystalline cellulose and derivative thereof; starch and hydrophilic derivatives thereof, or urethane.
Can be used for preparing the W/O that can be used to be prepared as theme of the present invention; O/W; W/O/W or O/W/O emulsion or comprise the guar gum protein extract; the example of the polyelectrolyte type polymer of the gelling water of the aqueous gel of its derivative or its hydrolysate is the multipolymer of vinylformic acid and 2-methyl-[(1-oxo-2-propenyl) amino]-1-propane sulfonic acid (AMPS); the multipolymer of acrylamide and 2-methyl-[(1-oxo-2-propenyl) amino]-1-propane sulfonic acid; the multipolymer of 2-methyl-[(1-oxo-2-propenyl) amino]-1-propane sulfonic acid and vinylformic acid 2-hydroxy methacrylate; the homopolymer of 2-methyl-[(1-oxo-2-propenyl) amino]-1-propane sulfonic acid; acrylic acid homopolymer; the multipolymer of acryl ethyl-trimethyl salmiac and acrylamide; AMPS and vinylpyrrolidone copolymers; the multipolymer of vinylformic acid and alkyl acrylate; its carbochain comprises 10-30 carbon atom; the multipolymer of AMPS and alkyl acrylate, its carbochain comprise 10-30 carbon atom.This base polymer is respectively at name Simulgel
TMEG, Sepigel
TM305, Simulgel
TMNS, Simulgel
TM800, Simulgel
TMA, Simulgel
TMEPG, Simulgel
TMINS, Simulgel
TMFL, Sepigel
TM501, Sepigel
TM502, Sepiplus
TM250, Sepiplus
TM265, Sepiplus
TM400, Sepinov
TMEMT 10, Carbopol
TM, Ultrez
TM10, Aculyn
TM, Pemulen
TMTR1, Pemulen
TMTR2, Luvigel
TMEM, Salcare
TMSC91, Salcare
TMSC92, Salcare
TMSC95, Salcare
TMSC96, Flocare
TMET100, Flocare
TMET58, Hispagel
TM, Novemer
TMEC1, Aristoflex
TMAVC, Aristoflex
TMHBM, Rapithix
TMA60, Rapithix
TMA100, Cosmedia SP and Stabileze
TMSell for 06 time.
In the wax of the topical cosmetic composition of the complete N-acyl group protein hydrolysate that can be used for comprising the N-acyl group protein hydrolysate in any source and/or obtain by subject methods of the present invention; for example can mention beeswax, carnauba wax, gama wax, ouricury wax, Japan tallow, cork fibrous wax, sugar-cane wax, paraffin, montanin wax, Microcrystalline Wax, lanolin wax, ceresine, polyethylene wax, winterized stearin, organosilicon wax, vegetable wax, be solid Fatty Alcohol(C12-C14 and C12-C18) and lipid acid at ambient temperature, or be solid glyceryl ester at ambient temperature.
In the emulsifying agent of the topical cosmetic composition of the complete N-acyl group protein hydrolysate that can be used for comprising the N-acyl group protein hydrolysate in any source and/or obtain, can mention by subject methods of the present invention:
-optional alkoxylated alkyl group polysaccharide glycosides fatty ester is the methyl polysaccharide glycosides ester of ethoxylation, very especially for example respectively at Glucamate
TMLT and Glumate
TMPEG-120 methyl glucose trioleate that DOE 120 sells under one's name and PEG-120 methyl glucose dioleate;
-alkoxylated fats ester is for example at Crothix
TMThe PEG-150 pentaerythritol tetrastearate that DS53 sells under one's name and at Antil
TMThe 141 PEG-55 propylene glycol oleic acid esters of selling under one's name;
-comprise the carbamate of the polyalkylene glycol of aliphatic chain, for example at Elfacos
TMThe different Fo Erji diurethanes of the PPG-14 ethoxylated dodecyl alcohol that T211 sells under one's name (laurethisophoryl dicarbamate), or at Elfacos
TMThe PPG-14 Palmitoleyl alcohol polyethers 60 hexyl diurethaness that GT2125 sells under one's name (palmeth 60 hexyl dicarbamate);
-lipid acid, ethoxylated fatty acid, the fatty acid ester of sorbyl alcohol, the fatty acid ester of N.F,USP MANNITOL, ethoxylated fatty acid ester, polysorbate, polyglycerol ester, ethoxylized fatty alcohol, sucrose ester, APG, the mixture of sulfation and phosphated alcohol or APG and Fatty Alcohol(C12-C14 and C12-C18), it is described in french patent application 2 668 080,2 734 496,2 756 195,2 762 317,2 784 680,2 784 904,2 791 565,2 790 977,2 807 435,2 804 432, in 2 830 774 and 2 830 445, be selected from the combination of the emulsifying surfactant of APG, APG and Fatty Alcohol(C12-C14 and C12-C18) or Polyglycerine or polyoxyethylene glycol or polyol ester for example are used for french patent application 2 852 257,2 858 554, the combination of the poly-hydroxy stearic acid ester of polyoxyethylene glycol in 2 820 316 and 2 852 258 or Polyglycerine.
Example as the active substance of the complete N-acyl group protein hydrolysate associating that can obtain with the N-acyl group protein hydrolysate in any source and/or by subject methods of the present invention; can mention compound with shinny or decolorization; arbutin for example; kojic acid; quinhydrones; ellagic acid; vitamins C; the ascorbic acid phosphoric acid esters magnesium salts; polyphenol extract; Fructus Vitis viniferae extract; pine extract; the wine extraction thing; Fructus Canrii Albi extract; the pomace extract; the Sucus Mali pumilae extract; amino acid; peptide; the adequate proteins hydrolysate; the Partial Protein hydrolysate; polyvalent alcohol (for example glycerine or butyleneglycol); urea; pyrrolidone carboxylic acid or derivative that should acid; glycyrrhetinic acid; α-Hydagen B; sugar or sugar derivatives; the polysaccharide or derivatives thereof; alcohol acid such as lactic acid; VITAMIN; vitamin derivative such as Vogan-Neu; vitamin-E and derivative thereof; mineral; enzyme; coenzyme such as Coenzyme Q10 99.0; hormone is as " parahormone " material, for example Phyto-Age
TM, soybean extraction such as Raffermine
TM, wheat extract such as Tensine
TMOr Gliadine
TMPlant milk extract is as being rich in the extract of tannic acid, be rich in the extract of isoflavones or be rich in terpenic extract, the extract of fresh water or marine algae, the extract of marine plant, main wax (essentialwaxes), bacterial extract, mineral, common lipoidis, lipoidis such as ceramide or phosphatide, active substance with antiobesity action, caffeine or derivatives thereof for example has the active substance of anti-microbial activity or cleaning action to oily skin, active substance with excitation or stimulation performance is as Sepitonic
TMM3 or Physiogenyl
TM, panthenol and derivative thereof are as Sepieap
TMMP, anti-aging active substance such as Sepivinol
TMOr Sepivital
TM, active substance such as Aquaxyl preserve moisture
TM, Extramel
TMC or Manoliva
TM, " anti-light aging " active substance, described active substance has instant level and smooth or the effect of compacting, for example Sesaflash to skin
TM, the active substance such as the Phyto-Age of protection corium-epidermis boundary integrity
TM, improve extracellular matrix component synthetic active substance such as Sepitonic
TMM3 or Aquaxyl
TM, have the active active substance of fat-reducing, curing or draining, for example caffeine, theophylline, cyclic amp (cAMP), Adipoless
TMGreen tea, red sage, ginkgo, ivy, horse-chestnut, bamboo, ruscus aculeatus, Ruscus (butcher ' s broom), Herba Centellae, heath bell, Ramulus et Folium Spiraeae Salicifolia, black wrack, Rosmarinus officinalis, willow, Selinum pastinaca extract or Herba Potentillae Chinensis extract, on skin, produce the active substance of " heat " sensation, skin microcirculation activator (example: nicotinate) for example, or the product (example: menthol and derivative) that generation " cold " is felt on skin, the active substance that stem cell is had effect, to epidermis, corium, corium and cutaneous appendage (hair, nail, sebiferous gland, pore etc.) have the active substance of effect, or the skin flora is had the active substance of effect.
Example as the sun-screening agent of the complete N-acyl group protein hydrolysate associating that can obtain with the N-acyl group protein hydrolysate in any source and/or by subject methods of the present invention; can mention all at Cosmetics Directive 76/768/EEC; revised edition, those that present among the Annex VII.
Following examples explanation the present invention, however do not limit the present invention.
Embodiment 1: preparation N-capryloyl Padil (compound 1)
With flow velocity 88.1g/ minute aqueous sodium hydroxide solution (30 weight %, density ≈ 1.33), flow velocity is that to introduce internal capacity be in 0.5 liter the jacketed reactor to 72g/ minute capryl(yl)chloride (density ≈ 0.95) and the flow velocity Padil sodium solution that comprises following component (density ≈ 1.105) that is 280.4g/ minute simultaneously and with stirring: 2220g water, 412.5g Padil (5.5 moles), 337.5g sodium-chlor and 431.5g 30% aqueous sodium hydroxide solution (3.24 moles), cool off described reactor to keep 25-30 ℃ temperature of reaction.Acylation reaction is undertaken by the pH of control agent, makes if necessary to make its keep being less than or equal to 9 and more than or equal to 8 by the flow velocity of regulating sodium hydroxide solution.When the volume that occupies when reaction mixture reaches the working volume of reactor, it begins to flow in the precipitation reactor that is equipped with worm screw, two chucks, wherein first chuck is being introduced side precipitation is cooled to 25-30 ℃ temperature, therefore second chuck also promote it to flow in the outside with the thermal precipitation thing, simultaneously with phosphate aqueous solution (20 weight %; Density ≈ 1.11) introduce in the described reactor with 559.4g/ minute flow velocity.The neutralization of N-capryloyl Padil is undertaken by the pH of control precipitation reactor medium, makes by the flow velocity of regulating phosphoric acid solution if necessary it is remained to be less than or equal to 2 and more than or equal to 1.
Therefore, obtain the aq suspension of 6460g/ hour N-capryloyl Padil.
The throw out suspension that obtains flows into and is equipped with in the constant level jar of pH meter, uses parallel distribution then so that can guarantee filtering successional 200D control CRICKET
TMType filter or equivalent continuous washing are also filtered.Therefore, obtain about 828g/ hour wet N-capryloyl Padil, be dried, spraying drying if necessary is to prepare about 165g/ hour the powder or the dried N-capryloyl Padil of aggregate form.
By the sample of gc analysis final product, determine free sadly exist with concentration less than 1 weight %.
The above evidence is compared with the batch processes of prior art, uses the advantage of method for continuously acylating of the present invention as follows:
-do not have organic solvent such as acetone use to prevent side reaction:
Chloride of acid+sodium hydroxide → acid+sodium-chlor
By the pH and the temperature condition of stepless control reactor and precipitation reactor, make duration of contact between the may command reactant;
-preparation equivalent N-acylamino acid uses at the most little by 10
4(0.5 liter replaces 5m to reactor doubly
3).
During the submission date, never describe or hint these advantages and the technical scheme that can realize them in present patent application in the prior art.
Embodiment 2: preparation N-undecylene acyl group phenylalanine (compound 2)
By being similar to the method for embodiment 1, but use the sodium salt of phenylalanine to replace Sodium Glycinate and N-undecene acyl chloride to replace capryl(yl)chloride to carry out, obtain N-undecylene acyl group phenylalanine.
The embodiment of cosmetic formulations
Following embodiment illustrates compound 1 that use obtains by subject methods of the present invention and 2 cosmetic formulations.
Embodiment 3: the emulsion of preservative-free
Preparaton
A Montanov
TM?68：5.00％
Sweet almond oil: 5.00%
DL-alpha-tocopherol 0.05%
B water: be enough to reach 100% amount
Glycerine 5.00%
Compound 1:1.00%
Sodium hydroxide: 0.50%
C Sepigel
TM?305： 0.30％
D spices: 0.30%
Program
Under 70 ℃, heat B down with the A fusion and at 75 ℃.Under 70 ℃ in A with B emulsification, add C then.35 ℃ of components that add the D phase down.Regulate pH.
Embodiment 4: the washing lotion that is used for acne skin
Preparaton
A Montanox
TM?20DF：05.00％
Spices: 00.20%
B water: be enough to reach 100% amount
Sodium hydroxide: 0.50%
Compound 1:0.100%
Program
Spices is dissolved in Montanox
TM In 20.In compound 1 water-soluble/NaOH mixture.A is mixed with B.
Embodiment 5: the shampoo that is used for dandruff and squamous scalp care
Preparaton
A water: 20.00%
Compound 1:2.00%
32 weight % soda-lyes: 1.12%
B PEG-120 methyl glucose dioleate: 3.00%
28 weight % Zetesol NLs: 33.00%
Amonyl
TM?675SB： 4.70％
Proteol
TM?OAT： 5.00％
Spices: 0.20%
Water: be enough to reach 100% amount
Lactic acid: the amount that is enough to make pH=5.5
Sodium-chlor: the amount that is enough to reach 3000cps
Program
With the water heating, add soda and compound 1, before mixing tensio-active agent and other compositions, nonionic wax is fused in this mixture, make its cooling then, stir simultaneously.Regulate viscosity by adding sodium-chlor.
Embodiment 6: clean the gel of preservative-free that is used for sensitive skin
Preparaton
A compound 1:1.00%
48 weight % sodium hydroxide: 0.35%
Water: 20.00%
B Simulsol
TM?220TM： 3.00％
Water: 10.00%
Capigel
TM?98： 5.00％
Water: 10.00%
C Oronal
TM?LCG： 20.00％
D spices: 0.10%
Glycerine: 5.00%
Water: be enough to reach 100% amount
Sodium hydroxide: the amount that is enough to make pH=9.0
Lactic acid: the amount that is enough to make pH=5.5
Dyestuff: an amount of (qs)
Program
In the presence of sodium hydroxide, compound 1 is being dissolved in the hot water under 90 ℃.Add Simulsol
TM220TM also stirs, and adds Oronal then
TMLCG, and spices is pre-dispersed in the glycerine (D), water is supplemented to enough amounts then.Under lower temperature, in water, dilute Capigel
TM98, add then and mix.If necessary, regulate pH (about 9), and then acidifying (about 0.8% lactic acid) is to required pH.
Embodiment 7: the anti-aging breast frost of releiving that is used for sensitive skin
Preparaton
A Montanov
TM?202： 3.00％
Squalane: 5.00%
Sepicalm
TM?VG： 3.00％
B water: be enough to reach 100% amount
Compound 1:0.50%
32wt% sodium hydroxide: 0.10%
C Queensland nut oil (Macadamia
Ternifolia oil) and Chinese gooseberry seed oil 3.00%
(kiwi?seed?oil)：
Cyclomethicone: 3.00%
D Sepigel
TM?305： 2.00％
E Sepicide
TM?HB： 0.20％
Tocopherol: 0.10%
Spices: 0.10%
Sodium hydroxide: qs pH
Program
Heat water down at 80 ℃.Before being heated to 80 ℃,, add fatty phase then to wherein adding sodium hydroxide, compound 1.The emulsification several minutes adds silicone oil and vegetables oil then.About 70 ℃, introduce Sepigel
TM305.Cooling also adds Sepicide about 30 ℃
TMHB, spices and tocopherol.Re-adjustment final pH if necessary.
Embodiment 8: the frothy gel of preservative-free as mild as a dove
Preparaton
A compound 1:2.00%
24 weight % sodium hydroxide: 1.48%
Water: 20.00%
B Capigel
TM?98： 3.00％
Water: 10.00%
C Oronal
TM?LCG： 14.00％
Proteol
TM?OAT： 4.00％
Oramide
TM?DL200AF：3.00％
Spices: 0.10%
Glycerine: 5.00%
Water: be enough to reach 100% amount
Sodium hydroxide: the amount that is enough to make pH=9.5
Lactic acid: the amount that is enough to make pH=5.3
Program
In the presence of sodium hydroxide, compound 1 is being dissolved in the hot water under 90 ℃.In this solution (A), add ingredients listed among the C, add prediluted Capigel then
TM98 (B).Add an amount of water, at first by alkalization, regulate the preparaton that pH obtains about pH 5.3 by acidifying more subsequently then.
Embodiment 9: the height endurability nursing breast frost that is used for sensitive skin
Preparaton
A Montanov
TM?202： 5.00％
Plant squalane: 5.00%
Cocounut oil octanoate/decylate: 10.00%
B sodium magnesium silicate: 1.00%
Xanthan gum: 0.30%
C water: be enough to reach 100% amount
Compound 1:1.00%
Sodium hydroxide: the amount that is enough to make pH=5
D spices: 0.10%
Sepicide
TM?HB： 0.20％
Program
Under 80-85 ℃ with the fatty substance fusion of A phase.Heat the C phase down at 80-85 ℃.With powder (B: sodium magnesium silicate and xanthan gum) be dispersed in fat mutually in, then under 80-85 ℃ in A emulsification C.
Embodiment 10: the frothy gel of preservative-free
Preparaton
A Amonyl
TM?675SB： 16.00％
Oramix
TM?NS?10： 09.00％
PEG-120 methyl glucose dioleate: 04.00%
Spices: 00.50%
B hot water (80-90 ℃): 20.00%
Compound 1:02.00%
Propylene glycol: 05.00%
32 weight % sodium hydroxide: 01.00%
C water: be enough to reach 100% amount
32 weight % sodium hydroxide: the amount that is enough to make pH=5
Program
The component of A is mixed in order.The component of B is mixed in order.B is added among the A, then C.Re-adjustment final pH if necessary.
Embodiment 11: the clean face gel that is used for spot and blackhead
Preparaton
A Sepigel
TM?305： 4.00％
Triheptin: 4.00%
B compound 1:4.00%
Propylene glycol: be enough to reach 100% amount
Program
At high temperature compound 1 is dissolved in the propylene glycol.After the cooling B added mutually gradually A mutually in, continuously stirring simultaneously.
Embodiment 12: the bright skin nursing emulsion that is used for ripe skin
Montanov
TM?202： 2.00％
Montanov
TM?68： 2.00％
Sad Triglyceride DDD: 10.00%
Squalane: 10.00%
Water: be enough to reach 100% amount
Compound 2:1.00%
Sepigel
TM?305： 0.70％
Ascorbic acid phosphoric acid esters magnesium salts: 2.00%
Sepicide
TM?HB： 0.30％
Sepicide
TM?CI： 0.20％
Spices: 0.50%
Embodiment 13: the fastening nursing emulsion of bright skin
Montanov
TM?202： 3.00％
24 weight % sodium hydroxide: 0.06%
Ethylhexyl methoxy cinnamate: 6.00%
Lanol
TM?1688： 8.00％
Benzophenone-3:4.00%
Water: be enough to reach 100% amount
Compound 2:2.00%
Simulgel
TM?NS： 0.50％
Sepilift
TM?DPHP： 0.50％
Polydimethylsiloxane: 2.00%
Cyclomethicone: 2.00%
Arbutin: 0.30%
Sepicide
TM?HB： 0.30％
Sepicide
TM?CI： 0.20％
Spices: 0.10%
Embodiment 14: the bright skin with alpha hydroxy acid coagulates frost
Natvosol: 0.80%
Sad ethylhexyl: 5.00%
60 weight % Sodium.alpha.-hydroxypropionates: 14.00%
Water: be enough to reach 100% amount
Compound 2:3.00%
Sepigel
TM?305： 4.20％
Sepicide
TM?HB： 2.00％
Sepicide
TM?CI： 3.00％
Spices: 0.10%
Embodiment 15: bright skin nursing emulsion
Montanov
TM?L： 1.00％
Hexadecanol: 2.00%
Isodecyl Neopentanoate: 12.00%
Sad cetearyl alcohol acid esters: 10.00%
Glycerine: 3.00%
Water: be enough to reach 100% amount
Compound 2:1.00%
Simulgel
TM?EG： 2.00％
Kojic acid: 1.00%
Sepicide
TM?HB： 0.30％
Sepicide
TM?CI： 0.20％
Spices: 0.10%
Embodiment 16: bright skin liquid
Oramix
TM?CG110： 5.00％
Kathon
TM?CG： 0.08％
Water: be enough to reach 100% amount
Compound 2:1.00%
Spices: 0.10%
This washing lotion can be sold in bottle or immerse in the liniment.
Embodiment 17: muffin
A compound 2:2.00%
Micropearl
TM?M310： 5.00％
Mica: 50.00%
Talcum: 32.50%
Iron oxide yellow: 0.50%
B Sepicalm
TM?VG： 5.00％
C polydimethylsiloxane: 5.00%
Program
All powder (A phase) is weighed, and they are dry grinded in knife mill.Add B phase and the regeneration milling time mutually identical with A.Add C and also repeat the grinding operation mutually identical mutually with B.Therefore the powder applying pressure of preparation is that 120 Kenwall manual compression machine is pressed in the jar then.
Embodiment 18: " the clear saturating colour of skin (clear complexion) " liquid
A compound 2:2.00%
B Micropearl
TM?M310： 3.00％
Water: be enough to reach 100% amount
Ka Bomo (carbomer): 0.25%
Xanthan gum: 0.20%
C isononyl isononanoate: 5.00%
D Sepicide
TM?HB： 0.30％
Sepicide
TM?CI： 0.20％
Spices: 0.30%
DL alpha-tocopherol: 0.05%
E Trometamol: the amount that is enough to make pH=7.2
Program
Compound 2 is dissolved in the ethanol, stirs simultaneously, add Micropearl then
TMM310.Ka Bomo and xanthan gum be dispersed in the water and with C with stir add this B mutually in.Add the D phase, regulate final pH if necessary.
Being described as follows of commodity that is used for embodiment:
Montanov
TM68 is the emulsifying agent of being sold by SEPPIC based on the pure and mild cetearyl glucoside of cetearyl alcohol.
Sepigel 305
TMBe the thickening material and stablizer (the INCI name: polyacrylamide, C of selling by SEPPIC
13-14Isoparaffin, laureth-7 (Laureth-7))
Montanox
TM20DF is the solubilizing agent of being sold by SEPPIC based on polysorbate-20.
Amonyl
TM675SB is the whipping agent of being sold by SEPPIC based on cocamidopropyl propyl hydroxy sultaine.
Proteol
TMOat is the whipping agent of being sold by SEPPIC based on avenin amino acid laurate.
Simulsol
TM220TM is the whipping agent of being sold by SEPPIC based on the PEG-200 Vinlub.
Capigel
TM98 is thickening material and the stablizer of being sold by SEPPIC based on acrylate copolymer.
Oronal
TMLCG be by SEPPIC sell based on the lauric alcohol polyether thiourea acid esters (cocoeth sulfate) of na form and the whipping agent and the toxinicide of PEG-40 glyceryl cocoate.
Montanov
TM202 is the emulsifying agent of being sold by SEPPIC based on n-Eicosanol, behenyl alcohol and peanut glucoside.
Sepicalm
TMVG; (INCI name: palmityl Sodium proline and white pond lily flower extract) sold by SEPPIC.
Sepicide
TMHB: the mixture (sanitas) of phenoxyethyl alcohol, para methyl paraben, oxybenzene ethyl formate, propylparaben and the oxybenzene butyl formate of selling by SEPPIC.
Oramide
TMDL200AF is the whipping agent of being sold by SEPPIC based on coconut oleoyl amine DEA.
Oramix
TMNS 10 is the whipping agent of being sold by SEPPIC based on Plantacare 818.
Sepicide
TMCI is the sanitas of being sold by SEPPIC based on tetrahydroglyoxaline.
Lanol
TM1688 is the cetostearyl alcohol ethylhexoate of being sold by SEPPIC.
Simulgel
TMNS is the counter-rotating of the reverse certainly latex (self-invertible inverse latex) by the multipolymer of SEPPIC sale, for example international openly those (INCI names: Hydroxyethyl Acrylate/acryl dimethyl Sodium taurine salt multipolymer and squalane and polysorbate60) shown in the WO 99/36445.
Sepilift
TMDPHP is the two palmitoyl oxyprolines of being sold by SEPPIC.
Montanov
TML is based on C
14-C22Pure and mild C
12-C20The emulsifying agent of APG, as described in the European patent application EP 0 995 487 those.
Simulgel
TMEG is the counter-rotating of the reverse certainly latex by the multipolymer of SEPPIC sale, for example international openly WO 99/36445 described those (INCI: sodium acrylate/acryl dimethyl Sodium taurine salt multipolymer and isohexadecane and polysorbate80).
Oramix
TMCG110 is the whipping agent of being sold by SEPPIC based on octyl glucoside and Plantacare 818.
Kathon
TMCG serves as reasons
﹠amp; Methylisothiazolinone/methylchloroisothiazandnone that Haas sells.
Micropearl
TMM310 for sell by SEPPIC based on polymethylmethacrylate and be dispersed in powder in the oil, it has absorption and control oiliness energy.
Claims (12)
1. one kind in the continuously synthetic method of mixture that comprises at least one divalence functional unit's (M1) N-acyl compounds or comprise at least one divalence functional unit's (M1) N-acyl compounds of aqueous phase:
Wherein n represents to equal 0,1 or 2 integer, and R1 represents to comprise the saturated or undersaturated linearity or the branched aliphatic group of 1-17 carbon atom, and described method comprises:
Steps A: make the compound that comprises at least one divalence functional unit (M2) or comprise the mixture of at least one divalence functional unit's (M2) compound:
Wherein n aforementioned definition in the divalence functional unit (M1), M represents alkali metal atom, and formula (IV) acyl halide:
R1 aforementioned definition the among the divalence functional unit (M1) as described wherein, X represents halogen atom, or with the mixture of formula (IV) acyl halide in the aqueous solution and comprise at least one divalence functional unit's (M3) N-acyl compounds with formation greater than reaction under 7 the pH:
Wherein n, M and R1 or comprise the mixture of at least one divalence functional unit's (M3) N-acyl compounds as defined above;
Step B: N-acyl compounds that comprises at least one divalence functional unit (M3) that under less than 7 pH, obtains in steps A or the mixture hydrolysis that comprises at least one divalence functional unit's (M3) N-acyl compounds, to form described N-acyl compounds or the described mixture that comprises at least one divalence functional unit's (M1) N-acyl compounds that comprises at least one divalence functional unit (M1);
It is characterized in that: steps A is following carries out: making flow velocity is d
1The materials flow of described formula (IV) acyl halide, flow velocity be d
2Described mixture stream and the flow velocity that comprises at least one divalence functional unit's (M2) compound or comprise at least one divalence functional unit's (M2) compound be d
3Alkaline aqueous solution materials flow Continuous Contact As time goes on; while freeze mode (IV) acyl halide/comprise at least one divalence functional unit's (M2) compound mol ratio less than 1 and more than or equal to 0.75; keep the pH of medium to be less than or equal to 9.5 simultaneously, more particularly be less than or equal to 9 and more than or equal to 8.
2. the method for claim 1 is wherein by the pH of control reaction medium and the carrying out that come the chemical reaction of monitoring step A of the pH by adding alkaline aqueous solution conditioned reaction medium if necessary.
3. as each described method in claim 1 and 2, wherein carry out steps A, keep temperature simultaneously less than 35 ℃.
4. as each described method among the claim 1-3, wherein carry out step B, keep pH to be less than or equal to 2 simultaneously.
5. as each described method among the claim 1-4, wherein behind the step B for wash with water with filtration step B in the step C of gained throw out dispersion.
6. method as claimed in claim 5 wherein is the sedimentary step D of gained among the drying step C behind the step C.
7. as each described method in claim 5 and 6, wherein with gained drying precipitate and spraying drying among the step C to obtain powder.
8. as each described method among the claim 1-7, it is used for synthesis type (I) N-acyl group a-amino acid:
R1 aforementioned definition the among the divalence functional unit (M1) as described wherein, R2 represents hydrogen atom, or is selected from the group of methyl, benzyl, isobutyl-, 1-methyl-propyl or sec.-propyl, and R3 represents hydrogen atom or methyl,
Described method comprises:
Steps A: an alkali metal salt that makes formula (II) a-amino acid:
Wherein R2 and R3 define in the formula (I) and M represents alkali metal atom as described above, and formula (IV) acyl halide:
Wherein R1 represents to comprise the saturated or undersaturated linearity or the branched aliphatic group of 1-17 carbon atom, and X represents halogen atom, or reacts in the aqueous solution and under greater than 7 pH with the mixture of formula (IV) acyl halide, to form formula (III) compound:
Wherein M, R1, R2 and R3 as defined above, or the mixture of formula (III) compound;
Step B: under less than 7 pH with steps A in the mixture hydrolysis of gained formula (III) compound or formula (III) compound, to form described formula (I) N-acyl group a-amino acid or formula (I) N-acyl alpha-amino acid whose mixture.
9. method as claimed in claim 8, it is used for synthesis type (I ') N-capryloyl Padil:
Represent heptyl corresponding to R1 wherein, R2 and R3 represent the formula (I) of hydrogen atom separately, and described method comprises:
Steps A: make formula (II ') Sodium Glycinate:
Represent the formula (II) of sodium atom corresponding to M wherein, and capryl(yl)chloride (IV '):
Represent that corresponding to R1 wherein heptyl and X represent the formula (IV) of chlorine atom, in aqueous sodium hydroxide solution and greater than 8 and be less than or equal under 9.5 the pH and react, to form formula (III ') compound:
Represent heptyl corresponding to R1 wherein, M represents sodium atom, and R1 represents that heptyl and R2 and R3 represent the formula of hydrogen atom (III) separately;
Step B: under less than 2 pH with steps A in gained formula (III ') compound hydrolysis, to form described formula (I ') N-capryloyl Padil;
Step C: wash with water and filtration step B in the sedimentary water dispersion of gained; With
Step D: the dry and spraying with the moist precipitate thing that obtains among the step C, to obtain the N-capryloyl Padil of fine powder form.
10. as each described method among the claim 1-9, it is used for preparing the N-acylamino acid continuously, it is characterized in that being d with more than or equal to 0.8 and less than chloride of acid/amino acid molar ratio of 1 with flow velocity
2Amino acid solution, flow velocity be d
1Chloride of acid and flow velocity be d
3Aqueous sodium hydroxide solution introduce simultaneously in the reactor that is equipped with agitator, the feasible meticulous homogenizing that can obtain described reaction medium of described reactor, and its size makes the residence time of reaction medium in reactor that forms be less than or equal to 5 minutes, wherein described reaction medium is remained under the temperature that is less than or equal to 35 ℃, and the pH of described reaction medium is remained under the value of 8.5-9.5; Described reaction medium is transferred in the precipitation reactor that is equipped with worm screw, therein in order to flow velocity d
4The phosphate aqueous solution of introducing is handled described reaction medium, make and in described precipitation reactor, can keep being less than or equal to 2 pH, to form the sedimentary water dispersion of described amino acid at the end that flows through described precipitation reactor, then with its washing and filtration, if necessary with gained moist precipitate thing drying, spraying drying then.
11. one kind is carried out as the equipment of method as described in each among the claim 1-10, it comprises:
Be equipped with agitator (AG1) and be used to measure the jacketed reactor (RE1) of the device (TICRE1) of internal temperature, it can circulate in described chuck by refrigerant and control and regulate wherein temperature, and wherein said refrigerant cools off by recirculation in interchanger (E1);
Three container ZB1, ZB2 and ZB3, respectively by 3 pumps (P1), (P2) and compound, formula (IV) acyl halide and the alkaline aqueous solution that (P3) will comprise at least one divalence functional unit (M2) respectively continuously from wherein discharging;
Three liquid flow lines (1), (2) and (3), it can make reactant flow out from described container (ZB1), (ZB2) with (ZB3) and introduce described reactors (RE1) by 3 inlets that are arranged in reactor (RE1) bottom;
Be equipped with the precipitation reactor (PR1) of worm screw (AG2), it is connected on the inlet that is positioned at described reactor (RE1) top by liquid flow line (4), and be connected on the container (ZB4) by liquid flow line (5), to be intended to the acidic aqueous solution that in described precipitation reactor (PR1) hydrolysis comprises at least one divalence functional unit's (M3) compound by pump (P4) discharges from container (ZB4), wherein said precipitation reactor (PR1) adds cover with chuck in its first half part that is called that upstream half divides, described chuck can circulate in described chuck by refrigerant and control and regulate wherein temperature, and add cover by chuck in its second half part that is called that downstream half divides, described chuck can circulate in described chuck by heating fluid and control and regulate wherein temperature;
That can reclaim from described precipitation reactor (PR1) effusive throw out dispersion holds groove (R02), it is equipped with pH control device (PHR02), its in its tract by liquid flow line (6), (7) and (8) be connected the set filter (F1) that is arranged in parallel, (F2) and (F3) on, described strainer by pump (P5) with being connected of waterworks, can wash and filter by described and hold the throw out dispersion that groove (R02) produces; Described strainer (F1), (F2), (F3) are connected on the liquid flow line (9) of rising in described overflow of holding groove (R02) in the downstream.
12. the part N-acyl group protein hydrolysate that obtains by each described method among the claim 1-10, fully N-acyl group protein hydrolysate, N-acyl group a-amino acid or N-acyl group sarkosine in the makeup topical composition as the purposes of activeconstituents and/or vehicle.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0852006A FR2929275B1 (en) | 2008-03-28 | 2008-03-28 | PROCESS FOR THE CONTINUOUS SYNTHESIS OF AN N-ACYL COMPOUND INSTALLATION FOR IMPLEMENTING THE METHOD |
| FR0852006 | 2008-03-28 | ||
| PCT/FR2009/050310 WO2009118493A2 (en) | 2008-03-28 | 2009-02-27 | Method for the continuous synthesis of an n-acylated compound, and equipment for implementing said method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101981000A true CN101981000A (en) | 2011-02-23 |
Family
ID=40098342
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200980111317XA Pending CN101981000A (en) | 2008-03-28 | 2009-02-27 | Method for the continuous synthesis of an N-acylated compound, and equipment for implementing said method |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP2271614A2 (en) |
| CN (1) | CN101981000A (en) |
| FR (1) | FR2929275B1 (en) |
| WO (1) | WO2009118493A2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104254253A (en) * | 2012-03-30 | 2014-12-31 | 奇华顿股份有限公司 | -acylated methionine derivatives as food flavouring compounds |
| CN112479914A (en) * | 2020-11-24 | 2021-03-12 | 蚌埠丰原医药科技发展有限公司 | Device and method for continuously producing acetaminophen |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102126984B (en) * | 2010-12-30 | 2014-10-01 | 上海奥利实业有限公司 | Condensation production process and special device of N-long-chain acyl amino acid salt |
| CN104030940A (en) * | 2014-06-24 | 2014-09-10 | 齐鲁工业大学 | Synthesis method of N-propenoyl-amino acid chiral polymerizable monomer |
| DE102016104205A1 (en) * | 2016-03-08 | 2017-09-14 | Minasolve Germany Gmbh | Aqueous solutions of N-acyl amino acids |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2463779A (en) | 1947-08-26 | 1949-03-08 | Ernest B Kester | N-acylated derivatives of glutamic acid and process for preparing them |
| DE1493660C3 (en) * | 1964-03-13 | 1974-03-14 | Farbwerke Hoechst Ag, Vormals Meister Lucius & Bruening, 6000 Frankfurt | Use of mixing devices consisting of stationary and rotating parts for the continuous conversion of fatty acid chlorides with aminocarboxylic acids or aminosulfonic acids or their soluble salts |
| DD131467B1 (en) * | 1977-06-20 | 1979-10-31 | Horst Berthold | METHOD FOR THE CONTINUOUS PREPARATION OF ACYLTAURIDES |
| FR2676922B1 (en) | 1991-06-03 | 1995-01-20 | Givaudan Lavirotte | COSMETIC APPLICATIONS OF N-ACYL DERIVATIVES OF MIXTURES OF AMINO ACIDS DERIVED FROM VEGETABLE PROTEIN HYDROLYSATES. |
| JPH06256276A (en) * | 1993-03-02 | 1994-09-13 | Kao Corp | Production of n-long-chain acylamino acid salt |
| FR2705341B1 (en) * | 1993-05-17 | 1995-06-23 | Givauban Lavirotte | Process for the preparation of mixtures of N-acylated amino acids, mixtures of N-acylated alpha amino acids, and their uses |
| DE19540645A1 (en) * | 1995-10-31 | 1997-05-07 | Basf Ag | Process and device for the continuous production of N-acylaminocarboxylic acids and N-acylaminosulfonic acids and their alkali metal salts |
-
2008
- 2008-03-28 FR FR0852006A patent/FR2929275B1/en not_active Expired - Fee Related
-
2009
- 2009-02-27 CN CN200980111317XA patent/CN101981000A/en active Pending
- 2009-02-27 EP EP09725514A patent/EP2271614A2/en not_active Withdrawn
- 2009-02-27 WO PCT/FR2009/050310 patent/WO2009118493A2/en active Application Filing
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104254253A (en) * | 2012-03-30 | 2014-12-31 | 奇华顿股份有限公司 | -acylated methionine derivatives as food flavouring compounds |
| CN104254253B (en) * | 2012-03-30 | 2017-12-29 | 奇华顿股份有限公司 | N as food fragrance compound is acylated methionine derivatives |
| CN112479914A (en) * | 2020-11-24 | 2021-03-12 | 蚌埠丰原医药科技发展有限公司 | Device and method for continuously producing acetaminophen |
| CN112479914B (en) * | 2020-11-24 | 2023-05-09 | 蚌埠丰原医药科技发展有限公司 | Device and method for continuously producing acetaminophen |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2271614A2 (en) | 2011-01-12 |
| WO2009118493A2 (en) | 2009-10-01 |
| WO2009118493A3 (en) | 2009-11-26 |
| FR2929275A1 (en) | 2009-10-02 |
| FR2929275B1 (en) | 2011-09-23 |
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Application publication date: 20110223 |