CN102775317A - Method for preparing allyldimethyl dehydroabietyl ammonium chloride - Google Patents
Method for preparing allyldimethyl dehydroabietyl ammonium chloride Download PDFInfo
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- CN102775317A CN102775317A CN2012102477995A CN201210247799A CN102775317A CN 102775317 A CN102775317 A CN 102775317A CN 2012102477995 A CN2012102477995 A CN 2012102477995A CN 201210247799 A CN201210247799 A CN 201210247799A CN 102775317 A CN102775317 A CN 102775317A
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Abstract
The invention relates to a method for preparing allyldimethyl dehydroabietyl ammonium chloride. The allyldimethyl dehydroabietyl ammonium chloride is a cationic surfactant containing unsaturated active C=C double bond and dehydroabietylamine structure. The method comprises the following steps: dissolving dehydroabietylamine in an ethanol-acetonitrile composite solvent, and reacting with formic acid and formaldehyde to obtain N,N-dimethyldehydroabietylamine; in the presence of a composite polymerization inhibitor composed of 2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMP), p-hydroxyanisole and hydroquinone in a mass ratio of (0.01-10):(0.01-100):(0.01-10), reacting allyl chloride and the N,N-dimethyldehydroabietylamine at 10-90 DEG C for 5-120 hours to obtain crude allyldimethyl dehydroabietyl ammonium chloride; and finally, recrystallizing by using a composite solvent composed of chloroform, ethyl acetate, aether, dioxane and tetrahydrofuran in a mass ratio of (0.01-10):(0.001-12):(0.1-10):(0.001-16):(0.001-18), and carrying out vacuum drying to obtain the allyldimethyl dehydroabietyl ammonium chloride product of which the mass percentage is greater than 90%.
Description
Technical field
A kind of novel preparation that a kind of method for preparing allyl dimethyl base dehydrogenation fir ammonium chloride involved in the present invention is Surfactant Chemistry aspect, forest chemical field contains the cats product method of westvaco rosin amine structure.
Background technology
Rosin is that a kind of secretory product rosin by pine tree is handled the material that obtains through fractionation, also is a kind of natural resource with recyclability.As a kind of industrial chemicals, rosin has originate abundant, low-cost characteristics.The resinous acid that contains three Yuans phenanthrene ring structures that the rosiny staple is made up of abietic acid, come into leaves abietic acid and neoabietic acid etc.Because not only have carboxyl in the structure of these resinous acids, but also have unsaturated carbon-carbon double bond, this makes them can be converted into rosin derivatives such as rosin Amine D, dehydroabietylamine, rosin alcohol through chemical modification.Utilize the product that these rosin derivatives can further 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 sulphonate, utilize synthetic rosin Amine D Soxylat A 25-7 of rosin Amine D 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 the requirement that meets " green " tensio-active agent and " 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.One of typical rosin derivative of generating through chemical modification as rosin of dehydroabietylamine wherein; Not only kept rosin inherent good biodegradability properties and environment friendliness property, and the amino that exists in its structure and benzene ring structure make it have better reactivity worth, application performance and antioxidant property.
With the dehydroabietylamine is that raw material can prepare 4 types the tensio-active agent that comprises aniorfic surfactant, non-ionics, cationic surfactant and amphoterics.
Dehydroabietylamine neutralizes the AS that can directly obtain having the sulphonate structure again with alkali after reacting with chlorsulfonic acid; Through dehydroabietylamine and reacting ethylene oxide generate have the rosin derivative of pure amine structure after; Again with reactions such as chlorsulfonic acid, sulphur trioxide, oleums, can generate the AS that existing sulfuric ester structure in the molecular structure also has T 46155 and similar pure amine structure; After rosin derivative through having pure amine structure and toxilic acid reaction form corresponding toxilic acid monoesters, again with in the alkali and can obtain the carboxylic acid type AS; Through the addition reaction of sodium sulfite anhy 96 to the two keys of the maleic acid ester verivate that contains westvaco rosin amine structure and T 46155 structure, the mono succinate sulfonated ester that can obtain having dehydroabietylamine T 46155 structure.These ASs with westvaco rosin amine 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 through with the addition reaction of oxyethane; Can generate nonionogenic tenside N-T 46155 dehydroabietylamine or N with dehydroabietylamine and T 46155 chain structure; N-two polyoxy ethene dehydroabietylamines, and such nonionogenic tenside can be regulated their hydrophilic and oleophilic performance through the chain number of controlling its polyoxyethylene chain.N-T 46155 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 clean metal the surface, and can form film in the metallic surface after cleaning with protection and anti-corrosion function.N-T 46155 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 through generating the nonionogenic tenside that acid amides and polyol structure are arranged with the Gluconolactone reaction, and this tensio-active agent all has the natural biological degradation property and day by day receives people's attention owing to employed raw material.Dehydroabietylamine through with epichlorohydrin reaction after can generate with the reaction of diethylolamine or dialkylamine again and have dehydroabietylamine and diethylolamine or N, the nonionogenic tenside of the two alkyl replacement of N-structure.With the dehydroabietylamine is that the nonionogenic tenside that feedstock production obtains generally all has fabulous wetting and emulsifying property; And toxicity is also less; Skin and eyes are had no stimulation, can be used as sanitising agent, emulsifying agent, foaming agent, inhibiter and dyeing auxiliaries.
Dehydroabietylamine is through generating N with formaldehyde and formic acid effect, behind the N-dimethyl-rosin Amine D, can generate with chloroacetate reaction and has the amphoterics that is similar to betaine structure; Dehydroabietylamine also can be directly through generating the amphoterics with amino acid structure with the halogenated carboxylic acid effect.The amphoterics that contains the westvaco rosin amine structure has certain resistance to hard water, and the foam rich, and wetting power is stronger, and emulsifying property and detergency ability are all relatively good.Simultaneously, and the amphoterics that contains the westvaco rosin amine structure all have certain bacterinertness.
N, N-dimethyl-dehydroabietylamine then can through with halohydrocarbons reaction, directly make the amido in the rosin Amine D structure be converted into the quaternary ammonium structure.Dehydroabietylamine under the certain reaction condition through with epichlorohydrin reaction generate have N-(3-chloro-2-hydroxypropyl) dehydroabietylamine after, can generate 3-rosin amine-2-hydroxypropyl-trimethyl ammonium chloride with the Trimethylamine reaction again; Through N-(3-chloro-2-hydroxypropyl) dehydroabietylamine and pyridine reaction, can generate the cats product that contains pyridine and rosin Amine D structure.These cats products with westvaco rosin amine structure generally all have application performances such as good antistatic, emulsification, softness and bactericidal.
Allyl dimethyl base dehydrogenation fir ammonium chloride is a kind of quaternary ammonium salt that contains unsaturated active carbon-carbon double bond and westvaco rosin amine structure; Can be used as active cationic monomer and be used for the macromolecular compound modification that Mierocrystalline cellulose, starch, chitosan etc. contain active hydroxyl or amino; In these macromolecular compound structures, to introduce quaternary ammonium group, obtain the macromolecule cation compound of cellulose, starch or chitosan structure.Allyl dimethyl base dehydrogenation fir ammonium chloride can also generate polycation type tensio-active agent through direct polymerization.The macromolecule cation compound of these cellulose, starch or chitosan structure, and allyl dimethyl base dehydrogenation fir ammonium chloride direct polymerization generation polycation type tensio-active agent can be widely used in the production of daily chemical product, the arrangement processing of textiles, the purification of waste water, the fields such as preparation of agricultural chemicals.Allyl dimethyl base dehydrogenation fir ammonium chloride generally is through N, and the nucleophilic reaction between N-dimethyl-dehydroabietylamine and chlorallylene generates.But; Through chlorallylene and N; When N-dimethyl-dehydroabietylamine direct reaction prepares allyl dimethyl base dehydrogenation fir ammonium chloride; Often have the self-polymerization of chlorallylene and the reactions such as allyl dimethyl base dehydrogenation fir ammonium chloride copolymerization of chlorallylene and generation, this can cause existing in the product more polymkeric substance, also can influence the reactive behavior of allyl dimethyl base dehydrogenation fir ammonium chloride as active haplotype quaternary ammonium salt simultaneously.Therefore consider from the quality that improves allyl dimethyl base dehydrogenation fir ammonium chloride product better, the application performance aspect of improving allyl dimethyl base dehydrogenation fir ammonium chloride, be necessary to seek a kind of method that can reduce polymer content in the allyl dimethyl base dehydrogenation fir ammonium chloride.Proposed among the present invention in the presence of composite polymerzation inhibitor, through chlorallylene and N, N-dimethyl-dehydroabietylamine direct reaction, thus a step obtain the allyl dimethyl base dehydrogenation fir ammonium chloride product of high mass content.
In the triturating of allyl dimethyl base dehydrogenation fir ammonium chloride, contacted a lot about rosin and rosin Amine D 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 " (the household chemicals science, 2006, Vol.29, No.5), " rosin-based sodium sulfosuccinate diester synthetic and character " (chemical research and application; 2005, Vol.14, No.4), " Synthesis and Properties of Rosin-based Polyglucoside " (chemistry of forest product with industry, 2006; Vol.26, No.1), " rosinyl bis-quaternary ammonium salt cationic surfactant synthetic and performance " (fine chemistry industry, 2003, Vol.20; No.9), " rosin polyglycerol ester nonionogenic tenside synthetic and performance " (petrochemical complex, 2004, Vol.33, No.3), " the synthetic and performance study of rosin polyoxyethylene surfactant " (fine chemistry industry; 1999, Vol.16, No.3), " rosin polyoxyethylene glycol citrate tensio-active agent synthetic and performance study " (chemistry world; 2001, Vol.42, No.11), " rosin based tensio-active agent synthetic and use " (leather chemical industry; 2006, Vol.23, No.2), " Preparation and Properties of Dimeric Fatty Ac id/Polyethylene Glycol Polyester Terminated with Rosin Acid " (chemistry of forest product with 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), " rosin series surfactant synthetic and use " (daily chemical industry; 2004, Vol.34, No.2), " new synthesis method of rosin acyl glycocoll tensio-active agent " (chemistry world; 2007, Vol.48, No.5), " contain rosin skeleton betaines amphoterics synthetic " (daily chemical industry; 2007, Vol.37, No.3), " dehydrogenation abietyl novel beet bases amphoterics synthetic " (modern chemical industry; 2004, Vol.24, No.4), " acrylic acid modified rosin Soxylat A 25-7 sodium sulfonate synthetic " (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 " (the Shenyang Institute of Chemical Technology journal, 2001, Vol 15; No.1), " Improved preparation of aqueous solution of3-halo-2-hydroxypropyltrialkylammonium halide " (JP 04145054A2,1992-05-19), " Preparation of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride as intermediate for carnitine " (JP03232845A2,1991-10-16).
Summary of the invention
A kind of invention for preparing the method for allyl dimethyl base dehydrogenation fir ammonium chloride; Mainly be in order to solve through chlorallylene and N; N-dimethyl-dehydroabietylamine direct reaction prepares the chlorallylene autohemagglutination that exists in the allyl dimethyl base dehydrogenation fir ammonium chloride process and the reactions such as allyl dimethyl base dehydrogenation fir ammonium chloride copolymerization of chlorallylene and generation; Cause existing in the product more polymkeric substance; And the existence of polymkeric substance causes allyl dimethyl base dehydrogenation fir ammonium chloride to descend as the reactive behavior of active haplotype quaternary ammonium salt, and has influence on the problem of the aspects such as application performance of product.
In the presence of composite polymerzation inhibitor; Directly through chlorallylene and N; The reaction of N-dimethyl-dehydroabietylamine; To realize N; N-dimethyl-dehydroabietylamine quaternized, and obtain cation modifying at Mierocrystalline cellulose, starch and chitosan, and disperse at pesticidal emulsifiable, dyestuff, active cationic surfactant allyl dimethyl base dehydrogenation fir ammonium chloride that metallic surface cleaning and a plurality of fields such as protection, processing of farm products and protection could be widely used and have good restraining and sterilizing bacteria and antistatic property.The allyl dimethyl base dehydrogenation fir ammonium chloride product that generates not only has good water-solubility, but also have that preparation cost is low, the characteristics such as content height of allyl dimethyl base dehydrogenation fir ammonium chloride in the product.Related a kind of method for preparing allyl dimethyl base dehydrogenation fir ammonium chloride in the invention; Its characteristics show as: effectively suppress the direct and N by chlorallylene through using composite polymerzation inhibitor; When reaction of N-dimethyl-dehydroabietylamine and step preparation allyl dimethyl base dehydrogenation fir ammonium chloride; The problem of copolymerization between the chlorallylene autohemagglutination that exists in the reaction process, chlorallylene and allyl dimethyl base dehydrogenation fir ammonium chloride and allyl dimethyl base dehydrogenation fir ammonium chloride autohemagglutination also makes the operation of preparation allyl dimethyl base dehydrogenation fir ammonium chloride more simple; The content of allyl dimethyl base dehydrogenation fir ammonium chloride is high in the product; Product can be water-soluble in the wide pH value scope.Allyl dimethyl base dehydrogenation fir ammonium chloride is similar with the quaternary ammonium salt cationic surfactant that contains the rosin Amine D 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 property and bio-surfactant concurrently, thereby the scope of application is also more extensive; Simultaneously owing to have active carbon carbon unsaturated double-bond in the allyl dimethyl base dehydrogenation fir ammonium chloride structure; But this can make its autohemagglutination film forming under certain condition, thereby can be used for the protection of metal through the allyl dimethyl base dehydrogenation fir ammonium chloride of related method preparation in the invention.In addition; In the allyl dimethyl base dehydrogenation fir ammonium chloride structure owing to there be quaternary ammonium salt structure and the ternary phenanthrene ring structure contain active carbon carbon unsaturated link(age); This not only can make it carry out the radical graft reaction, and to make it can show special stable emulsifying characteristic with hydroxyl, amino macromolecular compound.
Method through in the invention can realize chlorallylene and N, and the direct single step reaction ammonium of N-dimethyl-dehydroabietylamine obtains allyl dimethyl base dehydrogenation fir ammonium chloride product, and the content of allyl dimethyl base dehydrogenation fir ammonium chloride is higher than 90% in the product.
Description of drawings
Fig. 1 is the structural formula figure of the allyl dimethyl base dehydrogenation fir ammonium chloride that relates in the invention.
Fig. 2 is the FTIR figure of allyl dimethyl base dehydrogenation fir ammonium chloride.
Fig. 3 is an allyl dimethyl base dehydrogenation fir ammonium chloride
1H NMR figure.
The practical implementation method
A kind of method for preparing allyl dimethyl base dehydrogenation fir ammonium chloride that relates in the invention; Its process mainly comprises following components: (1) dehydroabietylamine (being also referred to as dehydroabietylamine) is used the double solvents dissolving that is made up of ethanol and acetonitrile, and forms the solution of homogeneous; (2) in the westvaco rosin amine aqueous solution, add aqueous formic acid, stir the solution that obtains containing the dehydroabietylamine formate; (3) in the solution that contains the dehydroabietylamine formate, add the methylation reaction reagent that constitutes by formaldehyde and Paraformaldehyde 96, and the reaction certain hour, obtain containing N, the mixture of N-dimethyl-dehydroabietylamine formate; (4) contain N, the mixture of N-dimethyl-dehydroabietylamine formate obtains containing N through neutralization, extracted in toluene, saturated common salt water washing, washing and separatory, the toluene solution of N-dimethyl-dehydroabietylamine; (5) contain N, the toluene solution of N-dimethyl-dehydroabietylamine carries out vacuum fractionation again behind normal pressure or underpressure distillation recovery toluene, obtain N, N-dimethyl-dehydroabietylamine; (6) N, N-dimethyl-dehydroabietylamine and composite polymerzation inhibitor with anhydrous alcohol solution after, drip chlorallylene again, and, obtain containing the mixture of allyl dimethyl base dehydrogenation fir ammonium chloride 10～90 ℃ of down reactions 5～120 hours; (7) mixture that contains allyl dimethyl base dehydrogenation fir ammonium chloride obtains thick allyl dimethyl base dehydrogenation fir ammonium chloride after absolute ethyl alcohol and excessive chlorallylene are reclaimed in underpressure distillation; (8) thick allyl dimethyl base dehydrogenation fir ammonium chloride is used the double solvents recrystallization that is made up of chloroform, ETHYLE ACETATE, ether, dioxane, THF; (9) material behind the recrystallization obtains allyl dimethyl base dehydrogenation fir ammonium chloride wet stock through cooling, crystallization, centrifugal or filtration; (10) allyl dimethyl base dehydrogenation fir ammonium chloride wet stock can obtain allyl dimethyl base dehydrogenation fir ammonium chloride product through vacuum-drying.
A kind of method for preparing allyl dimethyl base dehydrogenation fir ammonium chloride that relates in the invention; Its related process parameter is following: the double solvents of (1) dissolving dehydroabietylamine is 0.01～10: 0.01～17 formation by ethanol and acetonitrile by mass ratio, and the mass ratio of dehydroabietylamine and double solvents is 0.1～10: 0.01～10; (2) be that 0.1～10: 0.01～100 in the westvaco rosin amine aqueous solution, to add mass percentage concentration be 20%～95% aqueous formic acid by the mass ratio of dehydroabietylamine and aqueous formic acid; (3) mass ratio of formaldehyde and Paraformaldehyde 96 is 0.01～10: 0.01～15 in the methylation reaction reagent that is made up of formaldehyde and Paraformaldehyde 96 that in the solution that contains the dehydroabietylamine formate, adds; And the methylation reaction reagent that is made up of formaldehyde and Paraformaldehyde 96 and the mass ratio of dehydroabietylamine are 0.1～10: 0.01～20; Obtain contain N, the mixture of N-dimethyl-dehydroabietylamine formate in reaction under 20～90 ℃ after 0.5～72 hour by formaldehyde and Paraformaldehyde 96 methylation reaction reagent that constitutes and the solution that contains the dehydroabietylamine formate; (4) contain N, the mixture of N-dimethyl-dehydroabietylamine formate reclaims toluene and vacuum fractionation, the N that obtains, N-dimethyl-dehydroabietylamine through neutralization, extracted in toluene, saturated common salt water washing, washing and separatory, normal pressure or underpressure distillation; (5) press mass ratio 0.1～10: 0.001～10 with N; N-dimethyl-dehydroabietylamine with by tetramethyl-piperidyl oxygen (TEMP), MEHQ, Resorcinol by mass ratio 0.01～10: 0.01～100: 0.01～10 composite polymerzation inhibitor that constitutes mixes then uses anhydrous alcohol solution; Obtain containing N, the ethanol solution of N-dimethyl-dehydroabietylamine and composite polymerzation inhibitor; (6) press chlorallylene and N; The mass ratio of N-dimethyl-dehydroabietylamine is 0.01～10: 0.001～10 to containing N; Drip chlorallylene in the ethanol solution of N-dimethyl-dehydroabietylamine and composite polymerzation inhibitor; And under 10～90 ℃, reacted 5～120 hours, obtain containing the mixture of allyl dimethyl base dehydrogenation fir ammonium chloride; (7) mixture that contains allyl dimethyl base dehydrogenation fir ammonium chloride reclaims the thick allyl dimethyl base dehydrogenation fir ammonium chloride that obtains behind absolute ethyl alcohol and the excessive chlorallylene through underpressure distillation; Use by chloroform, ETHYLE ACETATE, ether, dioxane, THF by mass ratio 0.01～10: 0.001～12: 0.1～10: 0.001～16: 0.001～18 double solvents recrystallization that constitutes, and recrystallization to use the double solvents and the mass ratio of thick allyl dimethyl base dehydrogenation fir ammonium chloride be 1.0～20.0: 0.1～20.0; (8) material of recrystallization through cooling, crystallization, centrifugal or filter obtain allyl dimethyl base dehydrogenation fir ammonium chloride wet stock after; Be that 0.01～0.1MPa and temperature are to carry out vacuum-drying under 10～120 ℃ the condition in vacuum tightness again, the vacuum drying time is 1.0～48.0 hours; (9) in the product after the vacuum-drying allyl dimethyl base dehydrogenation fir ammonium chloride quality percentage composition greater than 90%.
Embodiment 1:
It is the double solvents dissolving formation homogeneous solution that constitutes at 0.01: 7 by mass ratio by ethanol and acetonitrile that 100 gram dehydroabietylamines use 400 grams; Add mass percentage concentration again and be 30% aqueous formic acid 600 grams, and stir and form the solution that contains the dehydroabietylamine formate; In the solution that contains the dehydroabietylamine formate, adding 50 grams is the methylation reaction reagent that constitutes at 1.0: 5.0 by formaldehyde and Paraformaldehyde 96 by mass ratio, and reacts 60 hours down at 40 ℃, obtains containing N, the mixture of N-dimethyl-dehydroabietylamine formate; Contain N; The mixture of N-dimethyl-dehydroabietylamine formate reclaims the N that obtains after toluene and the vacuum fractionation through neutralization, extracted in toluene, saturated common salt water washing, washing and separatory, normal pressure or underpressure distillation; N-dimethyl-dehydroabietylamine mixes the back with composite polymerzation inhibitor by mass ratio and uses anhydrous alcohol solution at 0.1: 0.001, and wherein composite polymerzation inhibitor is pressed 0.01: 1.0: 0.01 formation of mass ratio by tetramethyl-piperidyl oxygen (TEMP), MEHQ, Resorcinol; To containing N, Dropwise 50 restrains chlorallylene in the ethanol solution of N-dimethyl-dehydroabietylamine and composite polymerzation inhibitor, and reacts 72 hours down at 20 ℃, obtains containing the mixture of allyl dimethyl base dehydrogenation fir ammonium chloride; The mixture that contains allyl dimethyl base dehydrogenation fir ammonium chloride reclaims the thick allyl dimethyl base dehydrogenation fir ammonium chloride that obtains behind absolute ethyl alcohol and the excessive chlorallylene through underpressure distillation; Use by chloroform, ETHYLE ACETATE, ether, dioxane, THF by mass ratio 0.01: 12: 0.1: the double solvents recrystallization that constitutes at 6: 0.001, and recrystallization to use the double solvents and the mass ratio of thick allyl dimethyl base dehydrogenation fir ammonium chloride be 1.0: 0.1; The material of recrystallization obtains allyl dimethyl base dehydrogenation fir ammonium chloride wet stock through cooling, crystallization, centrifugal or filtration; Allyl dimethyl base dehydrogenation fir ammonium chloride wet stock is that 0.1MPa and temperature are under 60 ℃ the condition after dry 48 hours in vacuum tightness, promptly obtains allyl dimethyl base dehydrogenation fir ammonium chloride quality percentage composition and be 91% product.
Embodiment 2:
It is the double solvents dissolving formation homogeneous solution that constitutes at 0.1: 10 by mass ratio by ethanol and acetonitrile that 100 gram dehydroabietylamines use 800 grams; Add mass percentage concentration again and be 50% aqueous formic acid 900 grams, and stir and form the solution that contains the dehydroabietylamine formate; In the solution that contains the dehydroabietylamine formate, adding 100 grams is the methylation reaction reagent that constitutes at 7: 15 by formaldehyde and Paraformaldehyde 96 by mass ratio, and reacts 36 hours down at 70 ℃, obtains containing N, the mixture of N-dimethyl-dehydroabietylamine formate; Contain N; The mixture of N-dimethyl-dehydroabietylamine formate reclaims the N that obtains after toluene and the vacuum fractionation through neutralization, extracted in toluene, saturated common salt water washing, washing and separatory, normal pressure or underpressure distillation; N-dimethyl-dehydroabietylamine mixes the back with composite polymerzation inhibitor by mass ratio and uses anhydrous alcohol solution at 5.0: 0.01, and wherein composite polymerzation inhibitor is pressed 3: 0.3: 1 formations of mass ratio by tetramethyl-piperidyl oxygen (TEMP), MEHQ, Resorcinol; To containing N, drip 120 gram chlorallylenes in the ethanol solution of N-dimethyl-dehydroabietylamine and composite polymerzation inhibitor, and reacted 120 hours down at 60 ℃, obtain containing the mixture of allyl dimethyl base dehydrogenation fir ammonium chloride; The mixture that contains allyl dimethyl base dehydrogenation fir ammonium chloride reclaims the thick allyl dimethyl base dehydrogenation fir ammonium chloride that obtains behind absolute ethyl alcohol and the excessive chlorallylene through underpressure distillation; Use by chloroform, ETHYLE ACETATE, ether, dioxane, THF by mass ratio 3: 0.6: 7: the double solvents recrystallization that constitutes at 6: 1, and recrystallization to use the double solvents and the mass ratio of thick allyl dimethyl base dehydrogenation fir ammonium chloride be 10: 3; The material of recrystallization obtains allyl dimethyl base dehydrogenation fir ammonium chloride wet stock through cooling, crystallization, centrifugal or filtration; Allyl dimethyl base dehydrogenation fir ammonium chloride wet stock is that 0.1MPa and temperature are under 60 ℃ the condition after dry 24 hours in vacuum tightness, promptly obtains allyl dimethyl base dehydrogenation fir ammonium chloride quality percentage composition and be 92% product.
Embodiment 3:
It is that the double solvents dissolving that 3: 13 constitute forms homogeneous solution with acetonitrile by mass ratio by ethanol that 100 gram dehydroabietylamines use 1200 grams, add mass percentage concentration again and be 70% aqueous formic acid 900 grams, and stirring formation contains the solution of dehydroabietylamine formate; In the solution that contains the dehydroabietylamine formate, adding 150 grams is the methylation reaction reagent that constitutes at 5.0: 3 by formaldehyde and Paraformaldehyde 96 by mass ratio, and reacts 48 hours down at 60 ℃, obtains containing N, the mixture of N-dimethyl-dehydroabietylamine formate; Contain N; The mixture of N-dimethyl-dehydroabietylamine formate reclaims the N that obtains after toluene and the vacuum fractionation through neutralization, extracted in toluene, saturated common salt water washing, washing and separatory, normal pressure or underpressure distillation; N-dimethyl-dehydroabietylamine mixes the back with composite polymerzation inhibitor by mass ratio and uses anhydrous alcohol solution at 0.1: 0.01, and wherein composite polymerzation inhibitor is pressed 0.1: 3.0: 0.1 formation of mass ratio by tetramethyl-piperidyl oxygen (TEMP), MEHQ, Resorcinol; To containing N, drip 100 gram chlorallylenes in the ethanol solution of N-dimethyl-dehydroabietylamine and composite polymerzation inhibitor, and reacted 60 hours down at 50 ℃, obtain containing the mixture of allyl dimethyl base dehydrogenation fir ammonium chloride; The mixture that contains allyl dimethyl base dehydrogenation fir ammonium chloride reclaims the thick allyl dimethyl base dehydrogenation fir ammonium chloride that obtains behind absolute ethyl alcohol and the excessive chlorallylene through underpressure distillation; Use by chloroform, ETHYLE ACETATE, ether, dioxane, THF by mass ratio 0.1: 6: 3: the double solvents recrystallization that constitutes at 6: 0.1, and recrystallization to use the double solvents and the mass ratio of thick allyl dimethyl base dehydrogenation fir ammonium chloride be 10: 0.3; The material of recrystallization obtains allyl dimethyl base dehydrogenation fir ammonium chloride wet stock through cooling, crystallization, centrifugal or filtration; Allyl dimethyl base dehydrogenation fir ammonium chloride wet stock is that 0.1MPa and temperature are under 60 ℃ the condition after dry 24 hours in vacuum tightness, promptly obtains allyl dimethyl base dehydrogenation fir ammonium chloride quality percentage composition and be 92% product.
Embodiment 4:
It is the double solvents dissolving formation homogeneous solution that constitutes at 10: 13 by mass ratio by ethanol and acetonitrile that 100 gram dehydroabietylamines use 1600 grams; Add mass percentage concentration again and be 90% aqueous formic acid 800 grams, and stir and form the solution that contains the dehydroabietylamine formate; In the solution that contains the dehydroabietylamine formate, adding 180 grams is the methylation reaction reagent that constitutes at 5.0: 3 by formaldehyde and Paraformaldehyde 96 by mass ratio, and reacts 3 hours down at 90 ℃, obtains containing N, the mixture of N-dimethyl-dehydroabietylamine formate; Contain N; The mixture of N-dimethyl-dehydroabietylamine formate reclaims the N that obtains after toluene and the vacuum fractionation through neutralization, extracted in toluene, saturated common salt water washing, washing and separatory, normal pressure or underpressure distillation; N-dimethyl-dehydroabietylamine mixes the back with composite polymerzation inhibitor by mass ratio and uses anhydrous alcohol solution at 10: 0.01, and wherein composite polymerzation inhibitor is pressed 7: 87: 13 formations of mass ratio by tetramethyl-piperidyl oxygen (TEMP), MEHQ, Resorcinol; To containing N, drip 120 gram chlorallylenes in the ethanol solution of N-dimethyl-dehydroabietylamine and composite polymerzation inhibitor, and reacted 120 hours down at 10 ℃, obtain containing the mixture of allyl dimethyl base dehydrogenation fir ammonium chloride; The mixture that contains allyl dimethyl base dehydrogenation fir ammonium chloride reclaims the thick allyl dimethyl base dehydrogenation fir ammonium chloride that obtains behind absolute ethyl alcohol and the excessive chlorallylene through underpressure distillation; Use by chloroform, ETHYLE ACETATE, ether, dioxane, THF by mass ratio 1: 6: 3: the double solvents recrystallization that constitutes at 6: 10, and recrystallization to use the double solvents and the mass ratio of thick allyl dimethyl base dehydrogenation fir ammonium chloride be 18: 7; The material of recrystallization obtains allyl dimethyl base dehydrogenation fir ammonium chloride wet stock through cooling, crystallization, centrifugal or filtration; Allyl dimethyl base dehydrogenation fir ammonium chloride wet stock is that 0.05MPa and temperature are under 80 ℃ the condition after dry 36 hours in vacuum tightness, promptly obtains allyl dimethyl base dehydrogenation fir ammonium chloride quality percentage composition and be 94% product.
Embodiment 5:
It is the double solvents dissolving formation homogeneous solution that constitutes at 10: 17 by mass ratio by ethanol and acetonitrile that 100 gram dehydroabietylamines use 400 grams; Add mass percentage concentration again and be 80% aqueous formic acid 1000 grams, and stir and form the solution that contains the dehydroabietylamine formate; In the solution that contains the dehydroabietylamine formate, adding 160 grams is the methylation reaction reagent that constitutes at 3: 13 by formaldehyde and Paraformaldehyde 96 by mass ratio, and reacts 13 hours down at 70 ℃, obtains containing N, the mixture of N-dimethyl-dehydroabietylamine formate; Contain N; The mixture of N-dimethyl-dehydroabietylamine formate reclaims the N that obtains after toluene and the vacuum fractionation through neutralization, extracted in toluene, saturated common salt water washing, washing and separatory, normal pressure or underpressure distillation; N-dimethyl-dehydroabietylamine mixes the back with composite polymerzation inhibitor by mass ratio and uses anhydrous alcohol solution at 9: 0.01, and wherein composite polymerzation inhibitor is pressed 13: 77: 3 formations of mass ratio by tetramethyl-piperidyl oxygen (TEMP), MEHQ, Resorcinol; To containing N, drip 150 gram chlorallylenes in the ethanol solution of N-dimethyl-dehydroabietylamine and composite polymerzation inhibitor, and reacted 90 hours down at 70 ℃, obtain containing the mixture of allyl dimethyl base dehydrogenation fir ammonium chloride; The mixture that contains allyl dimethyl base dehydrogenation fir ammonium chloride reclaims the thick allyl dimethyl base dehydrogenation fir ammonium chloride that obtains behind absolute ethyl alcohol and the excessive chlorallylene through underpressure distillation; Use by chloroform, ETHYLE ACETATE, ether, dioxane, THF by mass ratio 10: 6: 3: the double solvents recrystallization that constitutes at 6: 3, and recrystallization to use the double solvents and the mass ratio of thick allyl dimethyl base dehydrogenation fir ammonium chloride be 18: 0.7; The material of recrystallization obtains allyl dimethyl base dehydrogenation fir ammonium chloride wet stock through cooling, crystallization, centrifugal or filtration; Allyl dimethyl base dehydrogenation fir ammonium chloride wet stock is that 0.075MPa and temperature are under 70 ℃ the condition after dry 36 hours in vacuum tightness, promptly obtains allyl dimethyl base dehydrogenation fir ammonium chloride quality percentage composition and be 93% product.
Claims (4)
1. method for preparing allyl dimethyl base dehydrogenation fir ammonium chloride; It is characterized in that: it is the double solvents dissolving of 0.01～10: 0.01～17 formation by mass ratio that dehydroabietylamine (being also referred to as dehydroabietylamine) uses by ethanol and acetonitrile; And after forming the solution of homogeneous; Be that 0.1～10: 0.01～100 in the westvaco rosin amine aqueous solution, to add mass percentage concentration be 20%～95% aqueous formic acid by the mass ratio of dehydroabietylamine and aqueous formic acid again, stir the solution that obtains containing the dehydroabietylamine formate; By the mass ratio of methylation reaction reagent and dehydroabietylamine is that 0.1～10: 0.01～20 in the solution that contains the dehydroabietylamine formate, to add by formaldehyde and Paraformaldehyde 96 be the methylation reaction reagent of 0.01～10: 0.01～15 formation by mass ratio; And under 20～90 ℃, reacted 0.5～72 hour; Obtain containing N, the mixture of N-dimethyl-dehydroabietylamine formate; Contain N, the mixture of N-dimethyl-dehydroabietylamine formate obtains containing N through neutralization, extracted in toluene, saturated common salt water washing, washing and separatory, the toluene solution of N-dimethyl-dehydroabietylamine; Contain N, the toluene solution of N-dimethyl-dehydroabietylamine carries out vacuum fractionation again behind normal pressure or underpressure distillation recovery toluene, obtain N, N-dimethyl-dehydroabietylamine; N; N-dimethyl-dehydroabietylamine with by tetramethyl-piperidyl oxygen (TEMP), MEHQ, Resorcinol by mass ratio 0.01～10: 0.01～100: 0.01～10 composite polymerzation inhibitor that constitutes mixes then uses anhydrous alcohol solution; Press chlorallylene and N again; The mass ratio of N-dimethyl-dehydroabietylamine is 0.01～10: 0.001～10 to containing N; Drip chlorallylene in the ethanol solution of N-dimethyl-dehydroabietylamine and composite polymerzation inhibitor, and reacted 5～120 hours down, obtain containing the mixture of allyl dimethyl base dehydrogenation fir ammonium chloride at 10～90 ℃; The mixture that contains allyl dimethyl base dehydrogenation fir ammonium chloride obtains thick allyl dimethyl base dehydrogenation fir ammonium chloride after absolute ethyl alcohol and excessive chlorallylene are reclaimed in underpressure distillation; Thick allyl dimethyl base dehydrogenation fir ammonium chloride is used by chloroform, ETHYLE ACETATE, ether, dioxane, THF by mass ratio 0.01～10: 0.001～12: 0.1～10: 0.001～16: 0.001～18 double solvents recrystallization that constitutes; Material behind the recrystallization is through cooling, crystallization, centrifugal or filter and obtain allyl dimethyl base dehydrogenation fir ammonium chloride wet stock; Allyl dimethyl base dehydrogenation fir ammonium chloride wet stock can obtain allyl dimethyl base dehydrogenation fir ammonium chloride product through vacuum-drying.
2. a kind of method for preparing allyl dimethyl base dehydrogenation fir ammonium chloride according to claim 1; It is characterized in that: N, N-dimethyl-dehydroabietylamine with by tetramethyl-piperidyl oxygen (TEMP), MEHQ, Resorcinol by mass ratio 0.01～10: the mass ratio of the composite polymerzation inhibitor of 0.01～100: 0.01～10 formation is 0.1～10: 0.001～10.
3. a kind of method for preparing allyl dimethyl base dehydrogenation fir ammonium chloride according to claim 1 is characterized in that: by chloroform, ETHYLE ACETATE, ether, dioxane, THF by mass ratio 0.01～10: it is 1.0～20.0: 0.1～20.0 that 0.001～12: 0.1～10: 0.001～16: 0.001～18 recrystallization that constitutes uses double solvents and mass ratio with thick allyl dimethyl base dehydrogenation fir ammonium chloride.
4. a kind of method for preparing allyl dimethyl base dehydrogenation fir ammonium chloride according to claim 1 is characterized in that: allyl dimethyl base dehydrogenation fir ammonium chloride quality percentage composition is greater than 90% in the product after the vacuum-drying.
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| CN108299914A (en) * | 2018-02-02 | 2018-07-20 | 广西科技项目评估中心 | A kind of electrostatic additive, preparation method and its usage for powdery paints |
| CN106008620B (en) * | 2016-05-30 | 2019-01-08 | 浙江工业大学 | A kind of dehydroabietic acid derivatives graft chitosan and the preparation method and application thereof |
| CN114561645A (en) * | 2022-01-25 | 2022-05-31 | 湖北菲特沃尔科技有限公司 | Polyoxyethylene rosin ammonium corrosion inhibitor and preparation method thereof |
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| CN114561645A (en) * | 2022-01-25 | 2022-05-31 | 湖北菲特沃尔科技有限公司 | Polyoxyethylene rosin ammonium corrosion inhibitor and preparation method thereof |
| CN114561645B (en) * | 2022-01-25 | 2023-12-19 | 湖北菲特沃尔科技有限公司 | Polyoxyethylene rosin ammonium corrosion inhibitor and preparation method thereof |
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