CN101508651A - Method for preparing 3-dehydroabietylamine-2-hydroxypropyl dimethyl benzyl ammonium chloride - Google Patents
Method for preparing 3-dehydroabietylamine-2-hydroxypropyl dimethyl benzyl ammonium chloride Download PDFInfo
- Publication number
- CN101508651A CN101508651A CNA2009101329941A CN200910132994A CN101508651A CN 101508651 A CN101508651 A CN 101508651A CN A2009101329941 A CNA2009101329941 A CN A2009101329941A CN 200910132994 A CN200910132994 A CN 200910132994A CN 101508651 A CN101508651 A CN 101508651A
- Authority
- CN
- China
- Prior art keywords
- dehydroabietylamine
- ammonium chloride
- dimethyl benzyl
- benzyl ammonium
- base
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A method for preparing 3-dehydroabietylamine-2-hydroxypropyl dimethyl benzyl ammonium chloride is a method for preparing a cationic active agent containing a rosin amine structure in the forest chemical field. At a temperature between 10 and 150 DEG C, an acid-binding agent compounded by sodium carbonate, potassium carbonate, calcium carbonate, sodium bicarbonate, potassium bicarbonate, potassium hydroxide, sodium hydroxide, triethylamine, tripropyl amine and tributyl amine is loaded on a carrier consisting of aluminum oxide, silica gel and active carbon to form a solid which is used as a catalyst for catalyzing the reaction of dehydroabietylamine and quaternizing agent consisting of epoxy propyl dimethyl benzyl ammonium chloride and 3-chlorin-2-hydroxypropyl dimethyl benzyl ammonium chloride for 1 to 50 hours, and then the reactants are subjected to centrifugation or filtration, exsolution and composite solvent recrystallization to form a wet material of the 3-dehydroabietylamine-2-hydroxypropyl dimethyl benzyl ammonium chloride; and the wet material is dried for 1.0 to 48.0 hours at a temperature between 10 and 120 DEG C at a vacuum degree of 0.01 to 0.1MPa to form a product of the 3-dehydroabietylamine-2-hydroxypropyl dimethyl benzyl ammonium chloride mass percentage of which is more than 90 percent.
Description
Technical field
The method of a kind of 3-of preparation dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride involved in the present invention is the cats product method that a kind of novel preparation of Surfactant Chemistry aspect, forest chemical field contains the dehydroabietylamine structure.
Background technology
Rosin is a kind of natural resource with recyclability, and as a kind of industrial chemicals, it also has, and the source is abundant, low-cost characteristics.The resinous acid that contains three Yuans phenanthrene ring structures that the rosiny main component is made up of abietic acid, come into leaves abietic acid and neoabietic acid etc.Because not only have carboxyl in the resinous acid, but also have unsaturated carbon-carbon double bond, this makes resinous acid can be converted into rosin derivatives such as dehydroabietylamine, rosin alcohol through chemical modification.Utilize the product that these rosin derivatives can synthesize a series of and lipid acid, aliphatic amide, the aliphatic alcohols surfactant structure is similar and show unique characteristics, as utilize sylvic acid to synthesize rosin ester sulfonate, utilize synthetic dehydroabietylamine Soxylat A 25-7 of dehydroabietylamine or rosin alcohol or rosin alcohol Soxylat A 25-7 etc.These are the surfactant product that feedstock production obtains with rosin, not only have good ecological performance and meet " green " tensio-active agent and the requirement of " raw material greenization ", and have good application performance, can be used as the production that emulsifying agent, washing composition, inhibiter, emulsion splitter, pigment dispersing agent, flocculation agent and flotation agent etc. are applied to multiple fine chemicals.Wherein one of typical rosin derivative of generating through chemical modification as rosin of dehydroabietylamine not only kept rosin inherent good biodegradability properties and environment friendliness, and the amino that exists in its structure makes it have better reactivity worth and application performance.
With the dehydroabietylamine is that raw material can prepare 4 types the tensio-active agent that comprises aniorfic surfactant, nonionic surface active agent, cationic surfactant and amphoterics.
Dehydroabietylamine by with chlorsulfonic acid reaction after again with in the alkali with the anion surfactant that can directly obtain having the sulfonate structure; By dehydroabietylamine and reacting ethylene oxide generate have the rosin derivative of pure amine structure after, can generate the anion surfactant that existing sulfuric ester structure in the molecular structure also has polyoxyethylene and similar pure amine structure with reactions such as chlorsulfonic acid, sulphur trioxide, oleums again; After rosin derivative by having pure amine structure and toxilic acid reaction form corresponding toxilic acid monoesters, again with in the alkali with can obtain the carboxylic acid type anion surfactant; By the addition reaction of sodium bisulfite to the two keys of the maleic acid ester derivative that contains dehydroabietylamine structure and polyoxyethylene structure, the mono succinate sulfonated ester that can obtain having dehydroabietylamine polyoxyethylene structure.These anion surfactants with dehydroabietylamine structure have good emulsification, dispersion, washing, wetting and characteristic of solubilizing, especially their mildness is all more superior than present most of anionic surfaces work or amphoterics, and safety performance is also very high.They can be widely used in industrial circles such as daily use chemicals industries such as washing, makeup and oil production, olefinic monomer letex polymerization, metal cleaning, textile printing and dyeing, sensitive materials.
Dehydroabietylamine by with the addition reaction of oxyethane, can generate nonionogenic tenside N-polyoxyethylene dehydroabietylamine or N with dehydroabietylamine and polyoxyethylene chain structure, N-two polyoxy ethene dehydroabietylamines, and such nonionogenic tenside can be regulated their hydrophilic and oleophilic performance by the chain number of controlling its polyoxyethylene chain.N-polyoxyethylene dehydroabietylamine or N; N-two polyoxy ethene dehydroabietylamines can be re-dubbed the aqueous solution that can be used as the metallic surface cleaning with rare nitric acid and diluted hydrofluoric acid; this aqueous solution not only can the clean metal surface, and can form the film with protection and anti-corrosion function in the metallic surface after cleaning.N-polyoxyethylene dehydroabietylamine or N, N-two polyoxy ethene dehydroabietylamines also have soft function, can be used as the dyeing auxiliary and the softening agent of leather industry.Dehydroabietylamine can also be by generating the nonionogenic tenside that acid amides and polyol structure are arranged with the Gluconolactone reaction, and this tensio-active agent day by day is subjected to people and payes attention to because employed raw material all has the natural biological degradation property.Dehydroabietylamine by with epichlorohydrin reaction after can generate with the reaction of diethanolamine or dialkylamine again and have dehydroabietylamine and diethanolamine or N, the two alkyl of N-replace the nonionogenic tenside of structure.Be that the feedstock production general wettability of nonionogenic tenside and the emulsifying property that obtain are fabulous with the dehydroabietylamine, and toxicity is less, skin and eyes are had no stimulation, and compounding capacity is strong, can be used as sanitising agent, emulsifying agent, foaming agent, inhibiter and dyeing auxiliaries.
Dehydroabietylamine is by generating N with formaldehyde and formic acid effect, behind the N-dimethyl dehydroabietylamine, can generate with chloroacetate reaction and has the amphoterics that is similar to betaine structure; Dehydroabietylamine also can be directly by generating the amphoterics with amino acid structure with the halogenated carboxylic acid effect.The amphoterics that contains the dehydroabietylamine structure has certain resistance to hard water, and foam is abundanter, and wetting power is stronger, and emulsifying property and detergency ability are all relatively good, and all has certain germ resistance.
Dehydroabietylamine by with the reaction of oxyethane and sulfuric acid dialkyl, can generate with quaternary ammonium structure and polyoxyethylene chain cationic surfactant as hydrophilic group; N, N-dimethyl dehydroabietylamine then can by with halohydrocarbons reaction, directly make the amido in the dehydroabietylamine structure be converted into the quaternary ammonium structure.Dehydroabietylamine has N-(3-chloro-2-hydroxypropyl) dehydroabietylamine by generating with epichlorohydrin reaction under the certain reaction condition, and then can generate 3-dehydroabietylamine base-2-hydroxypropyl-trimethyl ammonium chloride by the reaction of N-(3-chloro-2-hydroxypropyl) dehydroabietylamine and Trimethylamine, also can react the cats product that generation contain pyridine and dehydroabietylamine structure by N-(3-chloro-2-hydroxypropyl) dehydroabietylamine and pyridine.Numerous application performances such as that these cats products with dehydroabietylamine structure generally all have is antistatic preferably, emulsification, softness and bactericidal.But also exist more deficiency existing the preparation in the method that contains dehydroabietylamine structural cation tensio-active agent, wherein mainly shows the following aspects: the step of (1) reaction is many, and technology is comparatively complicated; (2) transformation efficiency of dehydroabietylamine is not high; (3) content of quaternary ammonium salt is not high in the product; (4) not very good because of existing more unreacted dehydroabietylamine to make the water-soluble of product in the product.Therefore consider from the using value of developing dehydroabietylamine better and the production cost aspect that reduces the cats product that contains the dehydroabietylamine structure, proposed in the present invention by dehydroabietylamine direct and 3-chloro-2-hydroxypropyl dimethyl benzyl ammonium chloride or the reaction of epoxypropyl dimethyl benzyl ammonium chloride in the presence of solid catalyst, thereby in dehydroabietylamine, introduce the quaternary ammonium group that contains the hydroxypropyl structure, and a step is produced 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride.
In the triturating of 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride, contacted a lot about rosin and dehydroabietylamine chemical modification and utilized the technical information of aspect, wherein have mainly comprising of certain reference value: " surfactivity of rosin alcohol Soxylat A 25-7 mono succinate sulfonated ester " (Nanjing University of Technology's journal, 2004, Vol.26, No.4), " progress of Abietyl modified tensio-active agent " (chemical industry progress, 2002, Vol.21, No.4), " Abietyl modified nonionogenic tenside progress " (household chemicals science, 2006, Vol.29, No.5), " the synthetic and character of rosin-based sodium sulfosuccinate diester " (chemical research and application, 2005, Vol.14, No.4), " Synthesis and Properties of Rosin2based Polyglucoside " (chemistry of forest product and industry, 2006, Vol.26, No.1), " the synthetic and performance of rosinyl bis-quaternary ammonium salt cationic surfactant " (fine chemistry industry, 2003, Vol.20, No.9), " the synthetic and performance of rosin polyglycerol ester nonionogenic tenside " (petrochemical complex, 2004, Vol.33, No.3), " the synthetic and performance study of rosin polyoxyethylene surfactant " (fine chemistry industry, 1999, Vol.16, No.3), " the synthetic and performance study of rosin polyoxyethylene glycol citrate tensio-active agent " (chemistry world, 2001, Vol.42, No.11), " the synthetic and application of rosin based tensio-active agent " (leather chemical industry, 2006, Vol.23, No.2), " Preparation and Properties of Dimeric Fatty Ac id/Polyethylene Glycol Polyester Terminatedwith Rosin Acid " (chemistry of forest product and industry, 2006, Vol.26, No.2), " rosin is the synthetic and development trend of stock chart surface-active agent " (chemistry of forest product industry, 1993, Vol.13, No.1), " the synthetic and application of rosin series surfactant " (daily chemical industry, 2004, Vol.34, No.2), " new synthesis method of rosin acyl glycine tensio-active agent " (chemistry world, 2007, Vol.48, No.5), " containing the synthetic of rosin skeleton betaines amphoterics " (daily chemical industry, 2007, Vol.37, No.3), " synthesizing of dehydrogenation abietyl novel beet bases amphoterics " (modern chemical industry, 2004, Vol.24, No.4), " synthesizing of acrylic acid modified rosin Soxylat A 25-7 sodium sulfonate " (daily chemical industry, 1999, Vol.29, No.4), " Preparation of cationic compounds as surfactants " (JP 06009521 A2,1994-01-18), " Study on the Synthesis of 3-Chloro-2-Hydroxypropyl Trialkylammonium Halide " (Shenyang Institute of Chemical Technology journal, 2001, Vol15, No.1), " Improved preparation of aqueous solution of3-halo-2-hydroxypropyltrialkylammonium halide " (JP 04145054 A2,1992-05-19), " Preparationof3-chloro-2-hydroxypropyl trimethyl ammonium chloride as intermediate for carnitine " (JP03232845 A2,1991-10-16).
Summary of the invention
A kind of invention for preparing the method for 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride mainly to be that the reactions steps that exists in existing quaternary ammonium salt cationic surfactant preparation method who contains the dehydroabietylamine structure and the technology is many, technology transformation efficiency comparatively complicated, dehydroabietylamine is not high in order solving, water-solublely not to be very good and to have influence on the problem of the aspects such as application performance of product because of what have that more unreacted dehydroabietylamine makes product in not high, the product of the content of quaternary ammonium salt in the product.
By being loaded with in the presence of the solid catalyst of acid binding agent; directly introduce on the amino in the dehydroabietylamine molecule band hydroxypropyl structure quaternary ammonium group, obtain disperseing, a plurality of fields such as production of metallic surface cleaning and protection, processing of farm products and protection, antibacterial bacteriostatic goods can be widely used and have the cats product 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride of good restraining and sterilizing bacteria and antistatic property at pesticidal emulsifiable, dyestuff.The 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride product that generates not only has good water-solubility and antibacterial bacteriostatic performance, and preparation cost also significantly reduces, good product quality.Related a kind of method for preparing 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride in the invention, its characteristics show as: directly prepare 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride by the single step reaction method, make the operation of reaction more simple; The use of the solid catalyst by being loaded with acid binding agent is improved the transformation efficiency of dehydroabietylamine; The reaction mass that contains 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride separates with byproduct with catalyzer easily; The content height of 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride in the product; Product can be water-soluble in the wide pH value scope.3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride is similar to the quaternary ammonium salt cationic surfactant that contains the dehydroabietylamine structure of other type, it all is the friendly type cats product of biodegradable ecology, in their molecular structure because the group of oleophylic performance is provided is the rosin structure, make its performance that can have natural sex and environment friendliness and bio-surfactant concurrently, thereby the scope of application is also more extensive; But simultaneously because the autohemagglutination film forming under certain condition of the carbon carbon unsaturated double-bond in three Yuans phenanthrene ring structures, this makes the 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride that obtains by related method in the invention can be used for the protection of metal.Simultaneously, there is the structure of similar Morpan BB in the molecular structure by 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride of obtaining of related method in the invention, thereby can be used as the production that antibiotic bacteriostat is used for the antibacterial bacteriostatic goods.Contain the quaternary ammonium salt structure and the ternary phenanthrene ring structure of hydroxypropyl in addition in 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride structure owing to existence, make it can show special stable emulsifying characteristic.
Method by in the invention can realize that dehydroabietylamine is converted into 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride product through single step reaction, and the content of 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride is higher than 90% in the product.
Description of drawings
Fig. 1 is the structural formula figure of 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride of relating in the invention.
Specific implementation method
The method of a kind of 3-of the preparation dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride that relates in the invention, its process mainly comprises following components: (1) dehydroabietylamine is dissolved in by 1,2-ethylene dichloride, methylene dichloride, ethyl acetate, chloroform, N, the double solvents that dinethylformamide, acetonitrile constitute, and form homogeneous solution; (2) in dehydroabietylamine solution, add the solid catalyst that is loaded with compound acid binding agent; (3) in the dehydroabietylamine solution that contains solid catalyst, add by epoxypropyl dimethyl benzyl ammonium chloride and 3-chloro-2-hydroxypropyl dimethyl benzyl ammonium chloride by certain mass than the quaternizing agent that constitutes, react the mixture that obtains containing 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride behind the certain hour; (4) mixture that contains 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride obtains containing the solution of 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride through centrifugal or filtration; (5) solution that contains 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride removes solvent through normal pressure or decompression, obtains containing the crude product of 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride; (6) contain the crude product double solvents recrystallization that constitutes by chloroform, ethyl acetate, ether, dioxane, tetrahydrofuran (THF) of 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride; (7) material behind the recrystallization is through cooling, crystallization, centrifugal or filter and obtain 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride wet stock; (8) 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride wet stock can obtain 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride product through vacuum-drying.
The method of a kind of 3-of the preparation dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride that relates in the invention, the processing parameter of its related preparation 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride is as follows: (1) is used to dissolve the double solvents of dehydroabietylamine by 1,2-ethylene dichloride, methylene dichloride, ethyl acetate, chloroform, N, dinethylformamide, acetonitrile are that 0.01～10:0.01～17:0.001～12:0.01～10:0～20:0～12 constitute by mass ratio; (2) carrier of the solid catalyst of Shi Yonging is made of by mass ratio 0.01～10:0.001～18:0～12 100～500 purpose aluminum oxide, 200～500 purpose silica gel, 100～500 purpose gacs; (3) acid binding agent is made of by mass ratio 0.1～10:0.01～12:0.01～10:0.001～16:0～18:0～10:0～10:0～8:0～5:0～7 yellow soda ash, salt of wormwood, lime carbonate, sodium bicarbonate, saleratus, potassium hydroxide, sodium hydroxide, triethylamine, tripropyl amine, Tributylamine; (4) solid catalyst that is loaded with acid binding agent is made of by mass ratio 0.01～10:0.01～100 acid binding agent, solid carrier; (5) quaternizing agent that is used for product preparation is made of by mass ratio 0.001～50:0.01～50 epoxypropyl dimethyl benzyl ammonium chloride and 3-chloro-2-hydroxypropyl dimethyl benzyl ammonium chloride; (6) temperature of dehydroabietylamine and quaternizing agent reaction is 10～150 ℃; (7) time of quaternizing agent such as dehydroabietylamine and epoxypropyl dimethyl benzyl ammonium chloride and/or 3-chloro-2-hydroxypropyl dimethyl benzyl ammonium chloride reaction is 1～50 hour; (8) mass ratio of dehydroabietylamine and solid catalyst is 0.05～50; (9) mass ratio of dehydroabietylamine and quaternizing agent is 0.1～5.0; When (10) dehydroabietylamine and quaternizing agent reacted, the mass ratio of double solvents and dehydroabietylamine was 1.0～25.0; (11) double solvents during recrystallization is made of by mass ratio 0.01～10:0.001～12:0.1～10:0.001～16:0.001～18 chloroform, ethyl acetate, ether, dioxane, tetrahydrofuran (THF); (12) during recrystallization, double solvents is 1.0～20.0 with the mass ratio that contains the crude product of 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride; (13) the 3-dehydroabietylamine base-vacuum tightness of 2-hydroxypropyl dimethyl benzyl ammonium chloride wet stock when carrying out vacuum-drying is that 0.01～0.1MPa, temperature are 10～120 ℃; (14) the vacuum drying time is 1.0～48.0 hours; (15) 3-dehydroabietylamine base in the product after the vacuum-drying-2-hydroxypropyl dimethyl benzyl ammonium chloride quality percentage composition is greater than 90%.
Embodiment 1:
100 gram dehydroabietylamines restrain by 1 with 400,2-ethylene dichloride, methylene dichloride, ethyl acetate, chloroform, N, dinethylformamide, acetonitrile are that the double solvents dissolving that 2:8:3:5:10:2 constitutes forms homogeneous solution by mass ratio, add the quaternizing agent that 100 grams are made of by mass ratio 10:13 epoxypropyl dimethyl benzyl ammonium chloride and 3-chloro-2-hydroxypropyl dimethyl benzyl ammonium chloride again, and stir the formation mixture; In mixture, add 50 and restrain the solid catalyst that is loaded with acid binding agent, wherein the carrier of solid catalyst is made of by mass ratio 1:2:3 100 purpose aluminum oxide, 300 purpose silica gel, 150 purpose gacs, and acid binding agent contained in the solid catalyst is made of by mass ratio 2:3:5:2:1:7:1:3:2:2 yellow soda ash, salt of wormwood, lime carbonate, sodium bicarbonate, saleratus, potassium hydroxide, sodium hydroxide, triethylamine, tripropyl amine, Tributylamine; Stirring also makes material carry out suction filtration to material in reaction under 30 ℃ again after 12 hours, obtains the solution of the clarifying 3-of containing dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride; To the solution that contains 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride revolve steam and fully remove the double solvents that dereaction uses after, obtain containing the crude product of 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride; The crude product double solvents recrystallization that constitutes by mass ratio 3:2:1:5:7 by chloroform, ethyl acetate, ether, dioxane, tetrahydrofuran (THF) that will contain 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride, double solvents is 3.0 with the mass ratio that contains the crude product of 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride during recrystallization; Material behind the recrystallization is through cooling, crystallization, centrifugal or filter the wet stock that obtains 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride; 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride wet stock is that 0.03MPa, drying temperature are under 30 ℃ the condition dry 12 hours in vacuum tightness again, and promptly obtaining 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride quality percentage composition is 91% product.
Embodiment 2:
100 gram dehydroabietylamines restrain by 1 with 800,2-ethylene dichloride, methylene dichloride, ethyl acetate, chloroform, N, dinethylformamide, acetonitrile are that the double solvents dissolving that 5:10:7:5:10:6 constitutes forms homogeneous solution by mass ratio, add the quaternizing agent that 300 grams are made of by mass ratio 1:13 epoxypropyl dimethyl benzyl ammonium chloride and 3-chloro-2-hydroxypropyl dimethyl benzyl ammonium chloride again, and stir the formation mixture; In mixture, add 150 and restrain the solid catalyst that is loaded with acid binding agent, wherein the carrier of solid catalyst is made of by mass ratio 2:7:9 300 purpose aluminum oxide, 300 purpose silica gel, 250 purpose gacs, and acid binding agent contained in the solid catalyst is made of by mass ratio 5:6:5:8:9:5:5:4:2:3 yellow soda ash, salt of wormwood, lime carbonate, sodium bicarbonate, saleratus, potassium hydroxide, sodium hydroxide, triethylamine, tripropyl amine, Tributylamine; Stirring also makes material carry out suction filtration to material in reaction under 70 ℃ again after 24 hours, obtains the solution of the clarifying 3-of containing dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride; To the solution that contains 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride revolve steam and fully remove the double solvents that dereaction uses after, obtain containing the crude product of 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride; The crude product double solvents recrystallization that constitutes by mass ratio 5:6:5:8:9 by chloroform, ethyl acetate, ether, dioxane, tetrahydrofuran (THF) that will contain 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride, double solvents is 10.0 with the mass ratio that contains the crude product of 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride during recrystallization; Material behind the recrystallization is through cooling, crystallization, centrifugal or filter the wet stock that obtains 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride; 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride wet stock is that 0.06MPa, drying temperature are under 70 ℃ the condition dry 20 hours in vacuum tightness again, and promptly obtaining 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride quality percentage composition is 93% product.
Embodiment 3:
100 gram dehydroabietylamines restrain by 1 with 1200,2-ethylene dichloride, methylene dichloride, ethyl acetate, chloroform, N, dinethylformamide, acetonitrile are that the double solvents dissolving that 8:3:9:5:12:3 constitutes forms homogeneous solution by mass ratio, add the quaternizing agent that 50 grams are made of by mass ratio 15:7 epoxypropyl dimethyl benzyl ammonium chloride and 3-chloro-2-hydroxypropyl dimethyl benzyl ammonium chloride again, and stir the formation mixture; In mixture, add 80 and restrain the solid catalyst that is loaded with acid binding agent, wherein the carrier of solid catalyst is made of by mass ratio 10:7:2 500 purpose aluminum oxide, 400 purpose silica gel, 400 purpose gacs, and acid binding agent contained in the solid catalyst is made of by mass ratio 10:3:7:16:1:9:2:1:1:7 yellow soda ash, salt of wormwood, lime carbonate, sodium bicarbonate, saleratus, potassium hydroxide, sodium hydroxide, triethylamine, tripropyl amine, Tributylamine; Stirring also makes material carry out suction filtration to material in reaction under 90 ℃ again after 8 hours, obtains the solution of the clarifying 3-of containing dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride; To the solution that contains 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride revolve steam and fully remove the double solvents that dereaction uses after, obtain containing the crude product of 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride; The crude product double solvents recrystallization that constitutes by mass ratio 10:2:1:12:7 by chloroform, ethyl acetate, ether, dioxane, tetrahydrofuran (THF) that will contain 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride, double solvents is 15.0 with the mass ratio that contains the crude product of 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride during recrystallization; Material behind the recrystallization is through cooling, crystallization, centrifugal or filter and obtain 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride wet stock; 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride wet stock is that 0.08MPa, drying temperature are under 90 ℃ of conditions dry 7 hours in vacuum tightness again, and promptly obtaining 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride quality percentage composition is 95% product.
Embodiment 4:
100 gram dehydroabietylamines restrain by 1 with 2000,2-ethylene dichloride, methylene dichloride, ethyl acetate, chloroform, N, dinethylformamide, acetonitrile are that the double solvents dissolving that 10:9:3:5:16:7 constitutes forms homogeneous solution by mass ratio, add the quaternizing agent that 150 grams are made of by mass ratio 15:1 epoxypropyl dimethyl benzyl ammonium chloride and 3-chloro-2-hydroxypropyl dimethyl benzyl ammonium chloride again, and stir the formation mixture; In mixture, add 160 and restrain the solid catalyst that is loaded with acid binding agent, wherein the carrier of solid catalyst is made of by mass ratio 10:2:7 450 purpose aluminum oxide, 300 purpose silica gel, 300 purpose gacs, and acid binding agent contained in the solid catalyst is made of by mass ratio 10:7:3:16:5:7:2:5:3:7 yellow soda ash, salt of wormwood, lime carbonate, sodium bicarbonate, saleratus, potassium hydroxide, sodium hydroxide, triethylamine, tripropyl amine, Tributylamine; Stirring also makes material carry out suction filtration to material in reaction under 110 ℃ again after 14 hours, obtains the solution of the clarifying 3-of containing dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride; To the solution that contains 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride revolve steam and fully remove the double solvents that dereaction uses after, obtain containing the crude product of 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride; The crude product double solvents recrystallization that constitutes by mass ratio 10:7:1:7:12 by chloroform, ethyl acetate, ether, dioxane, tetrahydrofuran (THF) that will contain 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride, double solvents is 20 with the mass ratio that contains the crude product of 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride during recrystallization; Material behind the recrystallization is through cooling, crystallization, centrifugal or filter and obtain 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride wet stock; 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride wet stock is that 0.10MPa, drying temperature are under 70 ℃ of conditions dry 6 hours in vacuum tightness again, and promptly obtaining 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride quality percentage composition is 97% product.
Embodiment 5:
100 gram dehydroabietylamines restrain by 1 with 1600,2-ethylene dichloride, methylene dichloride, ethyl acetate, chloroform, N, dinethylformamide, acetonitrile are that the double solvents dissolving that 9:10:5:3:16:12 constitutes forms homogeneous solution by mass ratio, add the quaternizing agent that 240 grams are made of by mass ratio 1:1 epoxypropyl dimethyl benzyl ammonium chloride and 3-chloro-2-hydroxypropyl dimethyl benzyl ammonium chloride again, and stir the formation mixture; In mixture, add 90 and restrain the solid catalyst that is loaded with acid binding agent, wherein the carrier of solid catalyst is made of by mass ratio 10:8:2 400 purpose aluminum oxide, 500 purpose silica gel, 500 purpose gacs, and acid binding agent contained in the solid catalyst is made of by mass ratio 10:12:10:16:18:10:10:8:5:7 yellow soda ash, salt of wormwood, lime carbonate, sodium bicarbonate, saleratus, potassium hydroxide, sodium hydroxide, triethylamine, tripropyl amine, Tributylamine; Stirring also makes material carry out suction filtration to material in reaction under 60 ℃ again after 48 hours, obtains the solution of the clarifying 3-of containing dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride; To the solution that contains 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride revolve steam and fully remove the double solvents that dereaction uses after, obtain containing the crude product of 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride; The crude product double solvents recrystallization that constitutes by mass ratio 10:1:9:8:18 by chloroform, ethyl acetate, ether, dioxane, tetrahydrofuran (THF) that will contain 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride, double solvents is 8 with the mass ratio that contains the crude product of 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride during recrystallization; Material behind the recrystallization is through cooling, crystallization, centrifugal or filter and obtain 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride wet stock; 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride wet stock is that 0.10MPa, drying temperature are dry 12 hours of 90 ℃ of conditions in vacuum tightness again, and promptly obtaining 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride quality percentage composition is 95.7% product.
Claims (10)
1, a kind of method for preparing 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride, it is characterized in that: in double solvents, reaction between the quaternizing agent that constitutes with the direct catalytic dehydrogenation abietyl amine of the solid catalyst that is loaded with compound acid binding agent and by epoxypropyl dimethyl benzyl ammonium chloride and 3-chloro-2-hydroxypropyl dimethyl benzyl ammonium chloride obtains containing the mixture of 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride; Contain the mixture of 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride, remove solvent after filtration or under centrifugation, normal pressure or the reduced pressure, obtain 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride crude product; 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride crude product obtains 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride product through double solvents recrystallization, vacuum-drying.
2, a kind of method for preparing 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride according to claim 1, it is characterized in that: 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride has following structural formula
3, a kind of method for preparing 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride according to claim 1, it is characterized in that: used catalyzer is that compound acid binding agent is carried on the solid catalyst that constitutes on the solid carrier during preparation 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride, and compound acid binding agent and carrier are to be 0.01～10:0.01～100 by mass ratio.
4, a kind of method for preparing 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride according to claim 1, it is characterized in that: double solvents used when dehydroabietylamine and quaternizing agent reaction is by 1,2-ethylene dichloride, methylene dichloride, ethyl acetate, chloroform, N, dinethylformamide, acetonitrile are that 0.01～10:0.01～17:0.001～12:0.01～10:0～20:0～12 constitute by mass ratio, and the mass ratio of double solvents and dehydroabietylamine is 1.0～25.0.
5, a kind of method for preparing 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride according to claim 1 is characterized in that: being used for the 3-dehydroabietylamine base-double solvents of 2-hydroxypropyl dimethyl benzyl ammonium chloride crude product recrystallization is to be made of by mass ratio 0.01～10:0.001～12:0.1～10:0.001～16:0.001～18 chloroform, ethyl acetate, ether, dioxane, tetrahydrofuran (THF); When recrystallization was handled 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride crude product, double solvents was 1.0～20.0 with the mass ratio that contains the crude product of 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride.
6, a kind of method for preparing 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride according to claim 1 is characterized in that: used quaternizing agent is to be made of by mass ratio 0.001～50:0.01～50 epoxypropyl dimethyl benzyl ammonium chloride, 3-chloro-2-hydroxypropyl dimethyl benzyl ammonium chloride during preparation 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride.
7, a kind of method for preparing 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride according to claim 1, it is characterized in that: during preparation 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride, the temperature of dehydroabietylamine and quaternizing agent reaction be time that 10～150 ℃, dehydroabietylamine and quaternizing agent react be that the mass ratio of 1～50 hour, dehydroabietylamine and solid catalyst is 0.05～50, the mass ratio of dehydroabietylamine and quaternizing agent is 0.1～5.0.
8, according to the described solid catalyst of claim 3, it is characterized in that: compound acid binding agent is made of by mass ratio 0.1～10:0.01～12:0.01～10:0.001～16:0～18:0～10:0～10:0～8:0～5:0～7 yellow soda ash, salt of wormwood, lime carbonate, sodium bicarbonate, saleratus, potassium hydroxide, sodium hydroxide, triethylamine, tripropyl amine, Tributylamine; The carrier of solid catalyst is made of by mass ratio 0.01～10:0.001～18:0～12 100～500 purpose aluminum oxide, 200～500 purpose silica gel, 100～500 purpose gacs.
9, a kind of method for preparing 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride according to claim 1 is characterized in that: the vacuum tightness during vacuum-drying is that 0.01～0.1Mpa, temperature are 10～120 ℃.
10, a kind of method for preparing 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride according to claim 1, it is characterized in that: the quality percentage composition of 3-dehydroabietylamine base-2-hydroxypropyl dimethyl benzyl ammonium chloride in product is greater than 90%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009101329941A CN101508651A (en) | 2009-03-30 | 2009-03-30 | Method for preparing 3-dehydroabietylamine-2-hydroxypropyl dimethyl benzyl ammonium chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009101329941A CN101508651A (en) | 2009-03-30 | 2009-03-30 | Method for preparing 3-dehydroabietylamine-2-hydroxypropyl dimethyl benzyl ammonium chloride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101508651A true CN101508651A (en) | 2009-08-19 |
Family
ID=41001203
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2009101329941A Pending CN101508651A (en) | 2009-03-30 | 2009-03-30 | Method for preparing 3-dehydroabietylamine-2-hydroxypropyl dimethyl benzyl ammonium chloride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101508651A (en) |
-
2009
- 2009-03-30 CN CNA2009101329941A patent/CN101508651A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101486657B (en) | Method for preparing 3-rosin amino-2-hydroxypropyl trimethyl ammonium chloride | |
| CN101475498B (en) | Preparation method of 3-dehydroabietylamine-2-hydroxypropyl trimethyl ammonium chloride | |
| CN101508650A (en) | Method for preparing 3-rosin amine-2-hydroxypropyl dimethyl benzyl ammonium chloride | |
| CN101941894A (en) | Cardanol polyoxyethylene ether and preparation method thereof | |
| CN103752210B (en) | Monomester succinate amino acid surfactant of functional amino groups and preparation method thereof | |
| CN115884748A (en) | Furan surfactant compositions and methods | |
| CN104059168B (en) | Allyldimethyl dehydroabietyl ammonium chloride graft shell oligose and preparation method thereof | |
| CN102775317A (en) | Method for preparing allyldimethyl dehydroabietyl ammonium chloride | |
| CN101016376B (en) | Method of synthesizing polyethylene glycol perfluoroolefin methyl ether | |
| CN100357266C (en) | Process for producing methyl carbamate | |
| CN101885745A (en) | Process for preparing glucoside sulfosuccinate ester salt by solvent-free method | |
| CN101249400B (en) | Maleated rosin based quaternaries cation surface active agent and method of preparing the same | |
| CN102093262A (en) | Octylphenol polyoxyethylene ether itaconic acid monoester sulfonic acid disodium salt and preparation method thereof | |
| US4476055A (en) | C21-Dicarboxylic acid isethionates as primary anionic surfactants | |
| CN106823984B (en) | A kind of abietyl tertiary amine class surfactant and its preparation method and application | |
| CN101508651A (en) | Method for preparing 3-dehydroabietylamine-2-hydroxypropyl dimethyl benzyl ammonium chloride | |
| CN106540632B (en) | A kind of protein based surfactants and preparation method thereof | |
| CN111378119B (en) | Ethylene oxide derivative with branched chain and tetrasulfonic acid group structure, method and application | |
| Su et al. | Surface activity and cleavability of gemini surfactants featuring hydrophilic spacer groups | |
| CN105664786B (en) | Anionic tall oil Gemini surface active agent and preparation method thereof | |
| KR20200056836A (en) | Di-alkyl glycerol based nonionic surfactants and preparation method thereof | |
| CN102643313A (en) | Heterogeneous secondary alcohol alkyl glycoside, and synthesis method and application thereof | |
| Janardhanan et al. | Synthesis and characterisation of sulfonated dimeric malenised soya fatty acid: a novel gemini surfactant | |
| CN216630776U (en) | Preparation device of composite surfactant | |
| Behler et al. | Nonionics as Intermediates for Ionic Surfactants |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Open date: 20090819 |