CN106905268A - A kind of Camphor Tree Seeds cationic emulsifier and its preparation method and application - Google Patents
A kind of Camphor Tree Seeds cationic emulsifier and its preparation method and application Download PDFInfo
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- CN106905268A CN106905268A CN201710148589.3A CN201710148589A CN106905268A CN 106905268 A CN106905268 A CN 106905268A CN 201710148589 A CN201710148589 A CN 201710148589A CN 106905268 A CN106905268 A CN 106905268A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/36—Compounds containing oxirane rings with hydrocarbon radicals, substituted by nitrogen atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
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- E—FIXED CONSTRUCTIONS
- E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
- E01C—CONSTRUCTION OF, OR SURFACES FOR, ROADS, SPORTS GROUNDS, OR THE LIKE; MACHINES OR AUXILIARY TOOLS FOR CONSTRUCTION OR REPAIR
- E01C7/00—Coherent pavings made in situ
- E01C7/08—Coherent pavings made in situ made of road-metal and binders
- E01C7/35—Toppings or surface dressings; Methods of mixing, impregnating, or spreading them
- E01C7/353—Toppings or surface dressings; Methods of mixing, impregnating, or spreading them with exclusively bituminous binders; Aggregate, fillers or other additives for application on or in the surface of toppings with exclusively bituminous binders, e.g. for roughening or clearing
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Abstract
The invention provides a kind of Camphor Tree Seeds cationic emulsifier and its preparation method and application.The present invention carries out hydrotreating to camphor tree seed oil, obtains the difatty acid of saturation ten；The difatty acid of the saturation ten and the propane diamine of N, N dimethyl 1,3 are carried out into condensation acylation reaction in mixed solution, amide intermediate is obtained；The mixed solution is the mixed solution of alkali metal hydroxide and toluene；By the amide intermediate in dry toluene with hcl reaction, obtain amide intermediate hydrochloride；The amide intermediate, amide intermediate hydrochloride and epichlorohydrin are heated, Camphor Tree Seeds cationic emulsifier is obtained.The present invention has not only expanded and has prepared the raw material of cationic emulsifier, reduces cost with camphor tree seed oil as raw material.Additionally, the emulsified asphalt that emulsifying agent provided by the present invention is obtained has excellent performance, softening point is about 81%, and elastic strength is about 97%, and adhesive strength is about 0.65MPa.
Description
Technical field
The present invention relates to cationic emulsifier technical field, more particularly to a kind of Camphor Tree Seeds cationic emulsifier and its preparation
Methods and applications.
Background technology
Asphalt emulsifier is the surfactant that can be used for asphalt emulsification, and the surface of water can be just made when minimal amount is added
Power is significantly reduced, and can substantially change the interfacial property and state of system, thus produce wetting, emulsification, foaming, washing, point
A series of effects such as scattered, antistatic, lubrication and solubilization, to reach the requirement of practical application.
Asphalt emulsifier can be divided into by ionic type classification：Anion emulsifier, cationic emulsifier, amphoteric emulsifier and
Nonionic emulsifier.Wherein, cationic emulsifier is in practice due to building stones cohesive more preferably, and materials are less, obtain
It is widely applied.In the prior art, cationic emulsifier mainly includes：Alkyl amine emulsifying agent, amide-type emulsifying agent, amination
Lignin emulsifying agent and quaternary ammonium salt emulsifying agent.
However, traditional pitch cationic emulsifier prepares limited source, and mostly chemical products, not only high cost,
Certain pollution can be also caused to environment.Camphor Tree Seeds are the fruits of canella camphor tree, so far, are not yet had in the prior art
The report of pitch cationic emulsifier is prepared as raw material with Camphor Tree Seeds.
The content of the invention
It is an object of the invention to provide a kind of Camphor Tree Seeds cationic emulsifier and its preparation method and application.The present invention with
Camphor tree seed oil prepares cationic emulsifier for raw material, can not only expand the raw material for preparing cationic emulsifier, additionally it is possible to rationally
Using Camphor Tree Seeds, waste is reduced.
In order to realize foregoing invention purpose, the present invention provides following technical scheme：
The invention provides a kind of preparation method of Camphor Tree Seeds cationic emulsifier, comprise the steps of：
(1) hydrotreating is carried out to camphor tree seed oil, obtains the difatty acid of saturation ten；
(2) difatty acid of the saturation ten and N, N- dimethyl -1,3- propane diamine are carried out into condensation acyl in mixed solution
Change reaction, obtain amide intermediate；
The mixed solution is the mixed solution of alkali metal hydroxide and toluene；
(3) by the amide intermediate in dry toluene with hcl reaction, obtain amide intermediate hydrochloride；
(4) amide intermediate, amide intermediate hydrochloride and epichlorohydrin are heated, is obtained Camphor Tree Seeds sun
Ionic emulsifying agent.
Preferably, volumetric concentration of the alkali metal hydroxide in mixed solution is 0.1~1%.
Preferably, in the step (2), the difatty acid of saturation ten and N, N- dimethyl -1, the mass ratio of 3- propane diamine is
1:(1~3)；
Volumetric concentration of the difatty acid of the saturation ten in mixed solution is 20~25%.
Preferably, the temperature of the condensation acylation reaction is 75~85 DEG C；
The time of the condensation acylation reaction is 10~20 hours.
Preferably, in terms of 1g amide intermediates, the flow velocity of the hydrogen chloride is 160~200mL/h.
Preferably, in the step (4), the mass ratio of amide intermediate, amide intermediate hydrochloride and epichlorohydrin is
(240~260):(290~310):(90~110).
Preferably, the temperature of the heating is 75~85 DEG C；
The time of the heating is 3~10 hours.
The invention provides the Camphor Tree Seeds cationic emulsifier that preparation method described in a kind of above-mentioned technical proposal is obtained.
Emulsified as emulsified asphalt the invention provides Camphor Tree Seeds cationic emulsifier described in a kind of above-mentioned technical proposal
The purposes of agent.
The invention provides the emulsified asphalt work that a kind of Camphor Tree Seeds cationic emulsifier as described in above-mentioned technical proposal is obtained
It is the application of pavement abrasion layer.
The invention provides a kind of Camphor Tree Seeds cationic emulsifier and its preparation method and application.The present invention is to camphor tree seed oil
Hydrotreating is carried out, the difatty acid of saturation ten is obtained；The difatty acid of the saturation ten and N, N- dimethyl -1,3- propane diamine are existed
Condensation acylation reaction is carried out in mixed solution, amide intermediate is obtained；The mixed solution is alkali metal hydroxide and toluene
Mixed solution；By the amide intermediate in dry toluene with hcl reaction, obtain amide intermediate hydrochloride；By institute
State amide intermediate, amide intermediate hydrochloride and epichlorohydrin to be heated, obtain Camphor Tree Seeds cationic emulsifier.This hair
It is bright with Camphor Tree Seeds as raw material, not only expanded and prepared the raw material of cationic emulsifier, cost reduced, simultaneously because reducing
The usage amount of work raw material, environmental protection reduces the pollution to environment.Additionally, the breast that emulsifying agent provided by the present invention is obtained
Changing pitch has excellent performance, and softening point is about 81%, and elastic strength is about 97%, and adhesive strength is about 0.65MPa.
Specific embodiment
The invention provides a kind of preparation method of Camphor Tree Seeds cationic emulsifier, comprise the steps of：
(1) hydrotreating is carried out to camphor tree seed oil, obtains the difatty acid of saturation ten；
(2) difatty acid of the saturation ten and N, N- dimethyl -1,3- propane diamine are carried out into condensation acyl in mixed solution
Change reaction, obtain amide intermediate；
The mixed solution is the mixed solution of alkali metal hydroxide and toluene；
(3) by the amide intermediate in dry toluene with hcl reaction, obtain amide intermediate hydrochloride；
(4) amide intermediate, amide intermediate hydrochloride and epichlorohydrin are heated, is obtained Camphor Tree Seeds sun
Ionic emulsifying agent.
The present invention carries out hydrotreating to camphor tree seed oil, obtains the difatty acid of saturation ten.The present invention is to the camphor tree seed oil
Source can be commercially available camphor tree seed oil without special requirement, specifically, or directly from Camphor Tree Seeds extraction camphor tree
Seed oil.The present invention originates without any particular/special requirement to the Camphor Tree Seeds, using source well known to those skilled in the art
Camphor Tree Seeds, it is specific as from adopting or commercially available.In the present invention, the Camphor Tree Seeds are preferably camphor tree green grass or young crops seed.In this hair
In bright, the oil content of the Camphor Tree Seeds is preferred >=and 40%, preferred >=45%, most preferably >=50%.
In the present invention, described extraction is preferably supercritical carbon dioxide extracting.In the present invention, the overcritical dioxy
The extraction temperature for changing carbon extraction is preferably 35~45 DEG C, most preferably more preferably 38~43 DEG C, 40 DEG C；The overcritical dioxy
The extracting pressure for changing carbon extraction is preferably 15~25MPa, most preferably more preferably 18~23MPa, 20MPa；It is described overcritical
The flow of the carbon dioxide of carbon dioxide abstraction is preferably 30~40kg/h, most preferably more preferably 33~38kg/h, 35kg/
h；The extraction time of the supercritical carbon dioxide extracting is preferably 100~120min, more preferably 105~112min, optimal
Elect 110min as.
The present invention does not have any particular/special requirement to the hydrotreating, using well-known to those skilled in the art organic
Thing method of hydrotreating is carried out.In the present invention, the hydrotreating is preferably atmospheric hydrogenation, i.e., in atmospheric conditions to camphor tree
Hydrogen is passed through in seed carries out hydrotreating.In the present invention, the flow of the hydroprocessing processes hydrogen is preferably 40~60mL/
Min, more preferably 45~55mL/min, most preferably 50mL/min.In the present invention, the hydrotreating is urged without catalyst
Changing to be carried out.
It is of the invention by the difatty acid of the saturation ten and N, N- dimethyl -1,3- after obtaining the difatty acid of the saturation ten
Propane diamine carries out condensation acylation reaction in mixed solution, obtains amide intermediate.In the present invention, the condensation acylation reaction
During the mass ratio of the difatty acid of saturation ten and N, N- dimethyl -1,3- propane diamine be preferably 1:(1~3), specifically can be with
It is 1:1、1:2 or 1:3.In the present invention, volumetric concentration of the difatty acid of the saturation ten in mixed solution be preferably 20~
25%, more preferably 21~24%, most preferably 22~23%.
In the present invention, the mixed solution is the mixed solution of alkali metal hydroxide and toluene.In the present invention, institute
State volumetric concentration of the alkali metal hydroxide in mixed solution and be preferably 0.1~1%, more preferably 0.3~0.8%, it is optimal
Elect 0.5% as.In the present invention, the alkali metal hydroxide is preferably potassium hydroxide or NaOH.
In the present invention, the temperature of the condensation acylation reaction is preferably 75~85 DEG C, more preferably 78~83 DEG C, optimal
Elect 80 DEG C as；The time of the condensation acylation reaction is preferably 10~20 hours, more preferably 12~18 hours, most preferably 15
Hour.
After the condensation acylation reaction, the product that acylation reaction is condensed described in preferred pair of the present invention carries out vacuum distillation, with
Toluene is removed, amide intermediate is obtained.The present invention does not have any particular/special requirement to the method and parameter of the vacuum distillation, adopts
With the vacuum distillation method of toluene well-known to those skilled in the art.
After the vacuum distillation, the solid matter for obtaining is washed present invention preferably uses carbonate solution, to remove
The difatty acid of unreacted saturation ten is removed, pure amide intermediate is obtained.In the present invention, the carbonate is preferably carbonic acid
Sodium or potassium carbonate；The mass concentration of the carbonate solution is preferably 0.1~5%, more preferably 0.5~3%, most preferably
1%.
In the present invention, the amide intermediate is mainly lauramide propyl-dimethyl tertiary amine.
After obtaining the amide intermediate, the present invention by the amide intermediate in dry toluene with hcl reaction,
Obtain amide intermediate hydrochloride.Being passed into hydrogen chloride gas in the present invention in the anhydrous toluene solution of amide intermediate is carried out
Reaction.In the present invention, in terms of 1g amide intermediates, the flow velocity of the hydrogen chloride is preferably 160~200mL/h, more preferably
170~190mL/h, most preferably 180mL/h.
The present invention does not have any particular/special requirement to the relative addition of the amide intermediate and dry toluene, can make
The amide intermediate that must be added is fully dissolved in dry toluene.Present invention selection, can using dry toluene as solvent
So that amide intermediate and hcl reaction is more abundant.
After the amide intermediate and hcl reaction, the product that preferred pair of the present invention is obtained carries out vacuum distillation, to remove
Toluene is removed, amide intermediate hydrochloride is obtained.The present invention do not have to the method and parameter of the vacuum distillation it is any it is special will
Ask, using the vacuum distillation method of toluene well-known to those skilled in the art.
After the vacuum distillation, the solid matter that preferred pair of the present invention is obtained is recrystallized, to obtain pure acid amides
Intermediate salt hydrochlorate.In the present invention, the recrystallization solvent is preferably ethyl acetate.In the present invention, the recrystallization
Number of times can be 1 time, 2 times, 3 times, 4 times or 5 times.
After obtaining the amide intermediate hydrochloride, the present invention by the amide intermediate, amide intermediate hydrochloride and
Epichlorohydrin is heated, and obtains Camphor Tree Seeds cationic emulsifier.In the present invention, in the middle of the amide intermediate, acid amides
The mass ratio of body hydrochloride and epichlorohydrin is preferably (240~260):(290~310):(90~110), more preferably (245~
255):(295~305):(95~105), most preferably 250:300:100.
In the present invention, the amide intermediate hydrochloride can with after soluble in water with amide intermediate HCI solution shape
Formula is added.The present invention does not have particular/special requirement to the concentration of the amide intermediate HCI solution, enables to the acyl
Amine intermediate salt hydrochlorate all dissolves.The amide intermediate is preferably dissolved in amide intermediate HCI solution by the present invention
Afterwards, epichlorohydrin is added.
In the present invention, the temperature of the heating is preferably 75~85 DEG C, more preferably 78~83 DEG C, most preferably
80℃；The time of the heating is preferably 3~10 hours, more preferably 4~8 hours, most preferably 5~6 hours.
Product after heating described in preferred pair of the present invention is removed water, and obtains Camphor Tree Seeds cationic emulsifier.At this
In invention, the water removal operation is preferably vacuum distillation water removal.The present invention does not have to the method and parameter of vacuum distillation water removal
There is any particular/special requirement, using the vacuum distillation method of water well-known to those skilled in the art.
After water removal, the solid product that preferred pair water removal of the present invention is obtained is recrystallized, to obtain pure Camphor Tree Seeds sun
Ionic emulsifying agent.In the present invention, the recrystallization solvent is preferably the mixed solvent of ethyl acetate and ethanol.In the present invention
In, the volume ratio of ethyl acetate and ethanol is preferably (22~26) in the mixed solvent:1, more preferably (23~25):1, most
Preferably 24:1.
Present invention also offers the Camphor Tree Seeds cationic emulsifier that preparation method described in a kind of above-mentioned technical proposal is obtained.
In the present invention, the Camphor Tree Seeds cationic emulsifier is faint yellow, solid material.
Present invention also offers Camphor Tree Seeds cationic emulsifier described in a kind of above-mentioned technical proposal as emulsified asphalt breast
The purposes of agent.The present invention does not have any spy to the preparation method for preparing emulsified asphalt by Camphor Tree Seeds cationic emulsifier
It is different to require, using the preparation method of emulsified asphalt well-known to those skilled in the art.
In the present invention, the method for preparing emulsified asphalt preferably comprises following steps：
Camphor Tree Seeds cationic emulsifier is soluble in water, and the pH value for adjusting solution is 2~3, obtains emulsifier aqueous solution；
Hot mixing is carried out to the emulsifier aqueous solution and pitch, emulsified asphalt is obtained.
In the present invention, the volumetric concentration of the aqueous solution of the Camphor Tree Seeds cationic emulsifier is preferably 15~20%, more
Preferably 16~19%, most preferably 17~18%.The present invention adjusts the Camphor Tree Seeds cationic galactomannan by adding sodium acid carbonate
The pH value of the aqueous solution of agent is 2~3, can be specifically 2,2.5 or 3.
After obtaining the emulsifier aqueous solution, the present invention carries out hot mixing to the emulsifier aqueous solution and pitch, obtains
Emulsified asphalt.Emulsifier aqueous solution described in preferred pair of the present invention mixes with pitch again after being preheated.In the present invention, it is described pre-
The temperature of heat is preferably 60~65 DEG C, most preferably more preferably 61~64 DEG C, 62~63 DEG C.Kind of the present invention to the pitch
Class does not have particular/special requirement, can be the pitch of any kind.In the present invention, the pitch is preferably modified SBS pitch.
In the present invention, the temperature of the hot mixing is preferably 130~135 DEG C, more preferably 131~134 DEG C, most preferably
It is 132~133 DEG C.In the present invention, the hot mixing is carried out preferably in colloid mill.In the present invention, the colloid mill
Rotating speed is preferably 60~100 revs/min, most preferably more preferably 70~90 revs/min, 80 revs/min；During the operation of the colloid mill
Between be preferably 0.5~2 hour, more preferably 1~1.5 hour.In the present invention, the solid content of the emulsified asphalt is preferably 30
~70%, more preferably 40~60%, most preferably 45~55%.
Present invention also offers emulsified asphalt described in a kind of above-mentioned technical proposal as pavement abrasion layer application.The present invention
There is no any particular/special requirement to the preparation method of pavement abrasion layer, the emulsified asphalt is coated on road surface.This
Invention does not have any particular/special requirement to the thickness of pavement abrasion layer, is configured according to different technical requirements.
Camphor Tree Seeds cationic emulsifier provided the present invention with reference to embodiment and its preparation method and application is carried out
Detailed description, but they can not be interpreted as limiting the scope of the present invention.
Embodiment 1
With camphor tree green grass or young crops seed as raw material, camphor tree seed oil is obtained through supercritical carbon dioxide extracting.Wherein, supercritical carbon dioxide
The temperature of extraction is 35 DEG C, and pressure is 15MPa, and carbon dioxide flow is 40kg/h, and the time is 100min.To the Camphor Tree Seeds for obtaining
Hydrogen is passed through in oil, in normal pressure, without catalyst under conditions of carry out hydrogenation reaction, obtain the difatty acid of saturation ten.
The difatty acid of saturation ten and N, N- dimethyl -1,3- propane diamine that will be obtained are 1 in mass ratio:2, containing 0.5%
In the toluene solution of the potassium hydroxide of (volume fraction), reacted 14 hours at 75 DEG C, decompression boils off toluene, obtains solid residue
Thing.Wherein, volumetric concentration of the difatty acid of the saturation ten in the toluene solution of potassium hydroxide is 20%.Mass fraction is used again
Aqueous sodium carbonate for 1% washs unreacted lauric acid/dodecanoic acid, obtains amide intermediate.
The amide intermediate that will be obtained is dissolved in dry toluene, continuous with the flow velocity of every gram of intermediate l80mL/h at room temperature
Hydrogen chloride gas are passed through, vacuum distillation afterwards removes toluene, obtains solid residue, then with re-crystallizing in ethyl acetate 3 times, obtained
Amide intermediate hydrochloride.
It is 250 by the mass ratio of amide intermediate, amide intermediate hydrochloride and epichlorohydrin:300:100 feed intake.In reaction
In device, amide intermediate hydrochloride is first dissolved in water, adds amide intermediate, after solution is transparent, add epichlorohydrin.80
Decompression boils off water after 6h is reacted at DEG C, is 24 with volume ratio:1 ethyl acetate alcohol solvent recrystallization, obtains faint yellow, solid
The Camphor Tree Seeds cationic emulsifier of shape.
Camphor Tree Seeds cationic emulsifier is soluble in water, and regulation pH value is 2, is heated to 63 DEG C, is added after mixing with 90# pitches
Heat prepares emulsified asphalt to 133 DEG C by colloid mill.
The mechanical property of the emulsified asphalt that the present invention is obtained to the present embodiment is tested, and as a result shows, emulsified asphalt
Softening point be 81%, elastic strength is 97%, and adhesive strength is 0.65MPa.
The emulsified asphalt that will be obtained prepares the thickness about ultra-thin wearing layer of pavement of 1cm, skid number>70BPN；
Significantly, section infiltration coefficient is 0 to water shutoff ability.
Embodiment 2
With camphor tree green grass or young crops seed as raw material, camphor tree seed oil is obtained through supercritical carbon dioxide extracting.Wherein, supercritical carbon dioxide
The temperature of extraction is 45 DEG C, and pressure is 25MPa, and carbon dioxide flow is 30kg/h, and the time is 120min.To the Camphor Tree Seeds for obtaining
Hydrogen is passed through in oil, in normal pressure, without catalyst under conditions of carry out hydrogenation reaction, obtain the difatty acid of saturation ten.
The difatty acid of saturation ten and N, N- dimethyl -1,3- propane diamine that will be obtained are 1 in mass ratio:1, containing 0.5%
In the toluene solution of the potassium hydroxide of (volume fraction), reacted 18 hours at 75 DEG C, decompression boils off toluene, obtains solid residue
Thing.Wherein, volumetric concentration of the difatty acid of the saturation ten in the toluene solution of potassium hydroxide is 23%.Mass fraction is used again
Aqueous sodium carbonate for 1% washs unreacted lauric acid/dodecanoic acid, obtains amide intermediate.
The amide intermediate that will be obtained is dissolved in dry toluene, continuous with the flow velocity of every gram of intermediate l75mL/h at room temperature
Hydrogen chloride gas are passed through, vacuum distillation afterwards removes toluene, obtains solid residue, then with re-crystallizing in ethyl acetate 3 times, obtained
Amide intermediate hydrochloride.
It is 255 by the mass ratio of amide intermediate, amide intermediate hydrochloride and epichlorohydrin:295:100 feed intake.In reaction
In device, amide intermediate hydrochloride is first dissolved in water, adds amide intermediate, after solution is transparent, add epichlorohydrin.85
Decompression boils off water after 6h is reacted at DEG C, is 26 with volume ratio:1 ethyl acetate alcohol solvent recrystallization, obtains faint yellow, solid
The Camphor Tree Seeds cationic emulsifier of shape.
Camphor Tree Seeds cationic emulsifier is soluble in water, and regulation pH value is 3, is heated to 65 DEG C, is added after mixing with 90# pitches
Heat prepares emulsified asphalt to 135 DEG C by colloid mill.
The mechanical property of the emulsified asphalt that the present invention is obtained to the present embodiment is tested, and as a result shows, emulsified asphalt
Softening point be 80.5%, elastic strength is 96.7%, and adhesive strength is 0.63MPa.
The emulsified asphalt that will be obtained prepares the thickness about ultra-thin wearing layer of pavement of 1cm, skid number>70BPN；
Significantly, section infiltration coefficient is 0 to water shutoff ability.
Embodiment 3
With camphor tree green grass or young crops seed as raw material, camphor tree seed oil is obtained through supercritical carbon dioxide extracting.Wherein, supercritical carbon dioxide
The temperature of extraction is 40 DEG C, and pressure is 20MPa, and carbon dioxide flow is 35kg/h, and the time is 110min.To the Camphor Tree Seeds for obtaining
Hydrogen is passed through in oil, in normal pressure, without catalyst under conditions of carry out hydrogenation reaction, obtain the difatty acid of saturation ten.
The difatty acid of saturation ten and N, N- dimethyl -1,3- propane diamine that will be obtained are 1 in mass ratio:2, containing 0.5%
In the toluene solution of the potassium hydroxide of (volume fraction), reacted 12 hours at 75 DEG C, decompression boils off toluene, obtains solid residue
Thing.Wherein, volumetric concentration of the difatty acid of the saturation ten in the toluene solution of potassium hydroxide is 25%.Mass fraction is used again
Aqueous sodium carbonate for 1% washs unreacted lauric acid/dodecanoic acid, obtains amide intermediate.
The amide intermediate that will be obtained is dissolved in dry toluene, continuous with the flow velocity of every gram of intermediate l85mL/h at room temperature
Hydrogen chloride gas are passed through, vacuum distillation afterwards removes toluene, obtains solid residue, then with re-crystallizing in ethyl acetate 3 times, obtained
Amide intermediate hydrochloride.
It is 245 by the mass ratio of amide intermediate, amide intermediate hydrochloride and epichlorohydrin:305:100 feed intake.In reaction
In device, amide intermediate hydrochloride is first dissolved in water, adds amide intermediate, after solution is transparent, add epichlorohydrin.75
Decompression boils off water after 6h is reacted at DEG C, is 23 with volume ratio:1 ethyl acetate alcohol solvent recrystallization, obtains faint yellow, solid
The Camphor Tree Seeds cationic emulsifier of shape.
Camphor Tree Seeds cationic emulsifier is soluble in water, and regulation pH value is 2, is heated to 60 DEG C, is added after mixing with 90# pitches
Heat prepares emulsified asphalt to 130 DEG C by colloid mill.
The mechanical property of the emulsified asphalt that the present invention is obtained to the present embodiment is tested, and as a result shows, emulsified asphalt
Softening point be 81%, elastic strength is 97%, and adhesive strength is 0.65MPa.
The emulsified asphalt that will be obtained prepares the thickness about ultra-thin wearing layer of pavement of 1cm, skid number>70BPN；
Significantly, section infiltration coefficient is 0 to water shutoff ability.
As seen from the above embodiment, the invention provides a kind of Camphor Tree Seeds cationic emulsifier and preparation method thereof and should
With.The present invention carries out hydrotreating to camphor tree seed oil, obtains the difatty acid of saturation ten；By the difatty acid of the saturation ten and N, N-
Dimethyl -1,3- propane diamine carries out condensation acylation reaction in mixed solution, obtains amide intermediate；The mixed solution is alkali
The mixed solution of metal hydroxides and toluene；By the amide intermediate in dry toluene with hcl reaction, obtain acyl
Amine intermediate salt hydrochlorate；The amide intermediate, amide intermediate hydrochloride and epichlorohydrin are heated, camphor tree is obtained
Seed cationic emulsifier.The present invention has not only expanded and has prepared the raw material of cationic emulsifier, reduces with camphor tree seed oil as raw material
Cost, simultaneously because reducing the usage amount of industrial chemicals, environmental protection reduces the pollution to environment.Additionally, by the present invention
The emulsified asphalt that the emulsifying agent of offer is obtained has excellent performance, and softening point is about 81%, and elastic strength is about 97%, viscosity
Intensity is about 0.65MPa.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of Camphor Tree Seeds cationic emulsifier, comprises the steps of：
(1) hydrotreating is carried out to camphor tree seed oil, obtains the difatty acid of saturation ten；
(2) difatty acid of the saturation ten and N, N- dimethyl -1,3- propane diamine are carried out into condensation in mixed solution to be acylated instead
Should, obtain amide intermediate；
The mixed solution is the mixed solution of alkali metal hydroxide and toluene；
(3) by the amide intermediate in dry toluene with hcl reaction, obtain amide intermediate hydrochloride；
(4) amide intermediate, amide intermediate hydrochloride and epichlorohydrin are heated, is obtained Camphor Tree Seeds cation
Emulsifying agent.
2. preparation method according to claim 1, it is characterised in that the alkali metal hydroxide is in mixed solution
Volumetric concentration is 0.1~1%.
3. preparation method according to claim 1, it is characterised in that in the step (2), the difatty acid of saturation ten and N,
The mass ratio of N- dimethyl -1,3- propane diamine is 1:(1~3)；
Volumetric concentration of the difatty acid of the saturation ten in mixed solution is 20~25%.
4. the preparation method according to claims 1 to 3 any one, it is characterised in that the temperature of the condensation acylation reaction
Spend is 75~85 DEG C；
The time of the condensation acylation reaction is 10~20 hours.
5. preparation method according to claim 1, it is characterised in that in terms of 1g amide intermediates, the stream of the hydrogen chloride
Speed is 160~200mL/h.
6. preparation method according to claim 1, it is characterised in that in the step (4), in amide intermediate, acid amides
The mass ratio of mesosome hydrochloride and epichlorohydrin is (240~260):(290~310):(90~110).
7. the preparation method according to claim 1 or 6, it is characterised in that the temperature of the heating is 75~85 DEG C；
The time of the heating is 3~10 hours.
8. the Camphor Tree Seeds cationic emulsifier that preparation method described in claim 1~7 any one is obtained.
9. Camphor Tree Seeds cationic emulsifier described in claim 8 as emulsified asphalt emulsifying agent purposes.
10. the emulsified asphalt for being obtained as Camphor Tree Seeds cationic emulsifier described in claim 9 as pavement abrasion layer application.
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|---|---|---|---|---|
| JP2000169719A (en) * | 1998-12-04 | 2000-06-20 | Kao Corp | Asphalt emulsion for slow set |
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| JP2000169719A (en) * | 1998-12-04 | 2000-06-20 | Kao Corp | Asphalt emulsion for slow set |
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| CN116768534A (en) * | 2023-08-16 | 2023-09-19 | 华运通达科技集团有限公司 | Cold mix asphalt mixture with high fatigue resistance and preparation method thereof |
| CN116768534B (en) * | 2023-08-16 | 2024-01-02 | 华运通达科技集团有限公司 | Cold mix asphalt mixture with high fatigue resistance and preparation method thereof |
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