CN106905268B - 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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- CN106905268B CN106905268B CN201710148589.3A CN201710148589A CN106905268B CN 106905268 B CN106905268 B CN 106905268B CN 201710148589 A CN201710148589 A CN 201710148589A CN 106905268 B CN106905268 B CN 106905268B
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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 present invention provides a kind of Camphor Tree Seeds cationic emulsifiers and its preparation method and application.The present invention carries out hydrotreating to camphor tree seed oil, obtains ten difatty acids of saturation；Ten difatty acids of the saturation and N, N- dimethyl -1,3- propane diamine are subjected to condensation acylation reaction in mixed solution, obtain amide intermediate；The mixed solution is the mixed solution of alkali metal hydroxide and toluene；The amide intermediate is obtained into amide intermediate hydrochloride with hcl reaction in dry toluene；The amide intermediate, amide intermediate hydrochloride and epichlorohydrin are heated, Camphor Tree Seeds cationic emulsifier is obtained.The present invention has not only expanded using camphor tree seed oil as raw material and has prepared the raw material of cationic emulsifier, reduces costs.In addition, the emulsified asphalt that emulsifier provided by the present invention obtains 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 preparations
Methods and applications.
Background technique
Asphalt emulsifier is the surfactant that can be used for asphalt emulsification, and the surface of water can be made when minimal amount is added
Power significantly reduces, and can substantially change the interfacial property and state of system, to generate wetting, emulsification, blistering, washing, divide
A series of effects such as scattered, antistatic, lubrication and solubilization, to reach the requirement of practical application.
Asphalt emulsifier by ionic type classification can be divided into: anion emulsifier, cationic emulsifier, amphoteric emulsifier and
Nonionic emulsifier.Wherein, cationic emulsifier is in practice due to more preferable with building stones adhesiveness, and materials are less, obtain
It is widely applied.In the prior art, cationic emulsifier specifically includes that alkyl amine emulsifier, amides emulsifier, amination
Lignin emulsifier and quaternary ammonium salt emulsifier.
However, traditional pitch cationic emulsifier prepares limited source, and mostly chemical products, it is not only at high cost,
Certain pollution can be also caused to environment.Camphor Tree Seeds are the fruits of lauraceae plant camphor tree, so far, in the prior art there has been no
The report of pitch cationic emulsifier is prepared using Camphor Tree Seeds as raw material.
Summary of the invention
The purpose of the present invention is to provide a kind of Camphor Tree Seeds cationic emulsifiers and its preparation method and application.The present invention with
Camphor tree seed oil is that raw material prepares cationic emulsifier, can not only expand the raw material for preparing cationic emulsifier, additionally it is possible to rationally
Using Camphor Tree Seeds, reduce waste.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of preparation methods of Camphor Tree Seeds cationic emulsifier comprising the steps of:
(1) hydrotreating is carried out to camphor tree seed oil, obtains ten difatty acids of saturation；
(2) ten difatty acids of the saturation and N, N- dimethyl -1,3- propane diamine are subjected to condensation acyl in mixed solution
Change reaction, obtains 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, obtains 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 mass ratio for being saturated ten difatty acids and N, N- dimethyl -1,3- propane diamine is
1:(1~3)；
Volumetric concentration of ten difatty acids of the saturation 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 intermediate, 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 heat treatment is 75~85 DEG C；
The time of the heat treatment is 3~10 hours.
The present invention provides the Camphor Tree Seeds cationic emulsifiers that preparation method described in a kind of above-mentioned technical proposal obtains.
The present invention provides Camphor Tree Seeds cationic emulsifiers described in a kind of above-mentioned technical proposal to emulsify as emulsified asphalt
The purposes of agent.
The present invention provides a kind of, and Camphor Tree Seeds cationic emulsifier obtains as described in above-mentioned technical proposal emulsified asphalt is made
For the application of pavement abrasion layer.
The present invention provides a kind of Camphor Tree Seeds cationic emulsifiers and its preparation method and application.The present invention is to camphor tree seed oil
Hydrotreating is carried out, ten difatty acids of saturation are obtained；Ten difatty acids of the saturation and N, N- dimethyl -1,3- propane diamine are existed
Condensation acylation reaction is carried out in mixed solution, obtains amide intermediate；The mixed solution is alkali metal hydroxide and toluene
Mixed solution；The amide intermediate is obtained into amide intermediate hydrochloride with hcl reaction in dry toluene；By institute
It states amide intermediate, amide intermediate hydrochloride and epichlorohydrin to be heated, obtains Camphor Tree Seeds cationic emulsifier.This hair
It is bright using Camphor Tree Seeds as raw material, not only expanded and prepared the raw material of cationic emulsifier, reduce costs, simultaneously because reducing
The usage amount of work raw material, it is environmentally protective, reduce the pollution to environment.In addition, the cream that emulsifier provided by the present invention obtains
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 present invention provides a kind of preparation methods of Camphor Tree Seeds cationic emulsifier comprising the steps of:
(1) hydrotreating is carried out to camphor tree seed oil, obtains ten difatty acids of saturation；
(2) ten difatty acids of the saturation and N, N- dimethyl -1,3- propane diamine are subjected to condensation acyl in mixed solution
Change reaction, obtains 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, obtains Camphor Tree Seeds sun
Ionic emulsifying agent.
The present invention carries out hydrotreating to camphor tree seed oil, obtains ten difatty acids of saturation.The present invention is to the camphor tree seed oil
Source there is no special requirement, specifically can be commercially available camphor tree seed oil, or the camphor tree directly extracted from Camphor Tree Seeds
Seed oil.The present invention does not have any particular/special requirement to the source of the Camphor Tree Seeds, using source well known to those skilled in the art
Camphor Tree Seeds, specifically as adopted certainly or commercially available.In the present invention, the Camphor Tree Seeds are preferably camphor tree blueness seed.In this hair
In bright, the oil contents of the Camphor Tree Seeds is preferred >=and 40%, preferred >=45%, most preferred >=50%.
In the present invention, described extract 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, more preferably 38~43 DEG C, most preferably 40 DEG C；The overcritical dioxy
The extracting pressure for changing carbon extraction is preferably 15~25MPa, more preferably 18~23MPa, most preferably 20MPa；It is described overcritical
The flow of the carbon dioxide of carbon dioxide abstraction is preferably 30~40kg/h, more preferably 33~38kg/h, most preferably 35kg/
h；The extraction time of the supercritical carbon dioxide extracting is preferably 100~120min, more preferably 105~112min, optimal
It is selected as 110min.
The present invention does not have any particular/special requirement to the hydrotreating, using well-known to those skilled in the art organic
Object method of hydrotreating carries out.In the present invention, the hydrotreating is preferably atmospheric hydrogenation, i.e., in atmospheric conditions to camphor tree
It is passed through hydrogen in seed and 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 can carry out.
After obtaining ten difatty acids of the saturation, the present invention is by ten difatty acids of the saturation and N, N- dimethyl -1,3-
Propane diamine carries out condensation acylation reaction in mixed solution, obtains amide intermediate.In the present invention, the condensation acylation reaction
It is saturated ten difatty acids and N in the process, the mass ratio of N- dimethyl -1,3- propane diamine is preferably 1:(1~3), it specifically can be with
For 1:1,1:2 or 1:3.In the present invention, volumetric concentration of ten difatty acids of the saturation 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
Stating volumetric concentration of the alkali metal hydroxide in mixed solution is preferably 0.1~1%, and more preferably 0.3~0.8%, it is optimal
It is selected as 0.5%.In the present invention, the alkali metal hydroxide is preferably potassium hydroxide or sodium hydroxide.
In the present invention, the temperature of the condensation acylation reaction is preferably 75~85 DEG C, more preferably 78~83 DEG C, optimal
It is selected as 80 DEG C；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 present invention is preferably evaporated under reduced pressure the product of the condensation acylation reaction, 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, present invention preferably uses carbonate solutions to wash obtained solid matter, to remove
Ten difatty acids of unreacted saturation are 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%, and 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.Hydrogen chloride gas is passed into the anhydrous toluene solution of amide intermediate in the present invention and is carried out
Reaction.In the present invention, in terms of 1g amide intermediate, 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 opposite additive amount of the amide intermediate and dry toluene, can make
The amide intermediate that must be added is fully dissolved in dry toluene.The present invention is selected using dry toluene as solvent, can
So that amide intermediate and hcl reaction more sufficiently.
After the amide intermediate and hcl reaction, the present invention is preferably evaporated under reduced pressure obtained product, to remove
Toluene is removed, amide intermediate hydrochloride is obtained.The present invention does not have any special want to the method and parameter of the vacuum distillation
It asks, using the vacuum distillation method of toluene well-known to those skilled in the art.
After the vacuum distillation, the present invention preferably recrystallizes obtained solid matter, to obtain pure amide
Intermediate salt hydrochlorate.In the present invention, the recrystallization is preferably ethyl acetate with solvent.In the present invention, the recrystallization
Number 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 Camphor Tree Seeds cationic emulsifier is obtained.In the present invention, the amide intermediate, among amide
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 heat treatment is preferably 75~85 DEG C, and more preferably 78~83 DEG C, most preferably
80℃；The time of the heat treatment is preferably 3~10 hours, more preferably 4~8 hours, most preferably 5~6 hours.
The present invention preferably removes water the product after the heat treatment, obtains Camphor Tree Seeds cationic emulsifier.At this
In invention, the water removal operation is preferably evaporated under reduced pressure water removal.The present invention does not have the method and parameter of the 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 the present invention preferably obtains water removal is recrystallized, to obtain pure Camphor Tree Seeds sun
Ionic emulsifying agent.In the present invention, the recrystallization is preferably the mixed solvent of ethyl acetate and ethyl alcohol with solvent.In the present invention
In, the volume ratio of the in the mixed solvent ethyl acetate and ethyl alcohol is preferably (22~26): 1, more preferably (23~25): 1, most
Preferably 24:1.
The present invention also provides the Camphor Tree Seeds cationic emulsifiers that preparation method described in a kind of above-mentioned technical proposal obtains.In
In the present invention, the Camphor Tree Seeds cationic emulsifier is faint yellow, solid material.
The present invention also provides Camphor Tree Seeds cationic emulsifiers described in a kind of above-mentioned technical proposal as emulsified asphalt cream
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, obtains emulsified asphalt.
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 addition sodium bicarbonate
The pH value of the aqueous solution of agent is 2~3, specifically can be 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.The present invention is mixed with pitch again after preferably preheating to the emulsifier aqueous solution.In the present invention, described pre-
The temperature of heat is preferably 60~65 DEG C, more preferably 61~64 DEG C, most preferably 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, and more preferably 131~134 DEG C, most preferably
It is 132~133 DEG C.In the present invention, the hot mixing carries out preferably in colloid mill.In the present invention, the colloid mill
Revolving speed is preferably 60~100 revs/min, more preferably 70~90 revs/min, most preferably 80 revs/min；When the operation of the colloid mill
Between 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%.
Application the present invention also provides emulsified asphalt described in a kind of above-mentioned technical proposal as pavement abrasion layer.The present invention
There is no any particular/special requirement to the preparation method of the pavement abrasion layer, the emulsified asphalt is coated on road surface.This
Invention does not have any particular/special requirement to the thickness of the pavement abrasion layer, is configured according to different technical requirements.
Camphor Tree Seeds cationic emulsifier provided by the invention and its preparation method and application is carried out below with reference to embodiment
Detailed description, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
Using camphor tree blueness 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, pressure 15MPa, carbon dioxide flow 40kg/h, time 100min.To obtained Camphor Tree Seeds
Hydrogen is passed through in oil, normal pressure, without catalyst under conditions of carry out hydrogenation reaction, obtain saturation ten difatty acids.
In mass ratio it is 1:2 by obtained ten difatty acid of saturation and N, N- dimethyl -1,3- propane diamine, is containing 0.5%
It in the toluene solution of the potassium hydroxide of (volume fraction), is reacted 14 hours at 75 DEG C, decompression boils off toluene, obtains solid residue
Object.Wherein, volumetric concentration of ten difatty acids of the saturation in the toluene solution of potassium hydroxide is 20%.Mass fraction is used again
Unreacted lauric acid/dodecanoic acid is washed for 1% aqueous sodium carbonate, obtains amide intermediate.
Obtained amide intermediate is dissolved in dry toluene, it is continuous with the flow velocity of every gram of intermediate l80mL/h at room temperature
It is passed through hydrogen chloride gas, vacuum distillation removes toluene later, obtains solid residue, then with re-crystallizing in ethyl acetate 3 times, obtain
Amide intermediate hydrochloride.
It feeds intake by the mass ratio of amide intermediate, amide intermediate hydrochloride and epichlorohydrin for 250:300:100.It is reacting
In device, amide intermediate hydrochloride is first dissolved in water, amide intermediate is added, after solution is transparent, epichlorohydrin is added.80
Decompression boils off water after reacting 6h at DEG C, is recrystallized with the ethyl acetate alcohol solvent that volume ratio is 24:1, obtains faint yellow, solid
The Camphor Tree Seeds cationic emulsifier of shape.
Camphor Tree Seeds cationic emulsifier is soluble in water, and adjusting pH value is 2, is heated to 63 DEG C, is added after mixing with 90# pitch
Heat prepares emulsified asphalt to 133 DEG C, by colloid mill.
The present invention is tested the mechanical property for the emulsified asphalt that the present embodiment obtains, the results show that emulsified asphalt
Softening point be 81%, elastic strength 97%, adhesive strength 0.65MPa.
Obtained emulsified asphalt is prepared into the ultra-thin wearing layer of pavement that thickness is about 1cm, skid number > 70BPN；
Water shutoff ability is significant, and section infiltration coefficient is 0.
Embodiment 2
Using camphor tree blueness 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, pressure 25MPa, carbon dioxide flow 30kg/h, time 120min.To obtained Camphor Tree Seeds
Hydrogen is passed through in oil, normal pressure, without catalyst under conditions of carry out hydrogenation reaction, obtain saturation ten difatty acids.
In mass ratio it is 1:1 by obtained ten difatty acid of saturation and N, N- dimethyl -1,3- propane diamine, is containing 0.5%
It in the toluene solution of the potassium hydroxide of (volume fraction), is reacted 18 hours at 75 DEG C, decompression boils off toluene, obtains solid residue
Object.Wherein, volumetric concentration of ten difatty acids of the saturation in the toluene solution of potassium hydroxide is 23%.Mass fraction is used again
Unreacted lauric acid/dodecanoic acid is washed for 1% aqueous sodium carbonate, obtains amide intermediate.
Obtained amide intermediate is dissolved in dry toluene, it is continuous with the flow velocity of every gram of intermediate l75mL/h at room temperature
It is passed through hydrogen chloride gas, vacuum distillation removes toluene later, obtains solid residue, then with re-crystallizing in ethyl acetate 3 times, obtain
Amide intermediate hydrochloride.
It feeds intake by the mass ratio of amide intermediate, amide intermediate hydrochloride and epichlorohydrin for 255:295:100.It is reacting
In device, amide intermediate hydrochloride is first dissolved in water, amide intermediate is added, after solution is transparent, epichlorohydrin is added.85
Decompression boils off water after reacting 6h at DEG C, is recrystallized with the ethyl acetate alcohol solvent that volume ratio is 26:1, obtains faint yellow, solid
The Camphor Tree Seeds cationic emulsifier of shape.
Camphor Tree Seeds cationic emulsifier is soluble in water, and adjusting pH value is 3, is heated to 65 DEG C, is added after mixing with 90# pitch
Heat prepares emulsified asphalt to 135 DEG C, by colloid mill.
The present invention is tested the mechanical property for the emulsified asphalt that the present embodiment obtains, the results show that emulsified asphalt
Softening point be 80.5%, elastic strength 96.7%, adhesive strength 0.63MPa.
Obtained emulsified asphalt is prepared into the ultra-thin wearing layer of pavement that thickness is about 1cm, skid number > 70BPN；
Water shutoff ability is significant, and section infiltration coefficient is 0.
Embodiment 3
Using camphor tree blueness 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, pressure 20MPa, carbon dioxide flow 35kg/h, time 110min.To obtained Camphor Tree Seeds
Hydrogen is passed through in oil, normal pressure, without catalyst under conditions of carry out hydrogenation reaction, obtain saturation ten difatty acids.
In mass ratio it is 1:2 by obtained ten difatty acid of saturation and N, N- dimethyl -1,3- propane diamine, is containing 0.5%
It in the toluene solution of the potassium hydroxide of (volume fraction), is reacted 12 hours at 75 DEG C, decompression boils off toluene, obtains solid residue
Object.Wherein, volumetric concentration of ten difatty acids of the saturation in the toluene solution of potassium hydroxide is 25%.Mass fraction is used again
Unreacted lauric acid/dodecanoic acid is washed for 1% aqueous sodium carbonate, obtains amide intermediate.
Obtained amide intermediate is dissolved in dry toluene, it is continuous with the flow velocity of every gram of intermediate l85mL/h at room temperature
It is passed through hydrogen chloride gas, vacuum distillation removes toluene later, obtains solid residue, then with re-crystallizing in ethyl acetate 3 times, obtain
Amide intermediate hydrochloride.
It feeds intake by the mass ratio of amide intermediate, amide intermediate hydrochloride and epichlorohydrin for 245:305:100.It is reacting
In device, amide intermediate hydrochloride is first dissolved in water, amide intermediate is added, after solution is transparent, epichlorohydrin is added.75
Decompression boils off water after reacting 6h at DEG C, is recrystallized with the ethyl acetate alcohol solvent that volume ratio is 23:1, obtains faint yellow, solid
The Camphor Tree Seeds cationic emulsifier of shape.
Camphor Tree Seeds cationic emulsifier is soluble in water, and adjusting pH value is 2, is heated to 60 DEG C, is added after mixing with 90# pitch
Heat prepares emulsified asphalt to 130 DEG C, by colloid mill.
The present invention is tested the mechanical property for the emulsified asphalt that the present embodiment obtains, the results show that emulsified asphalt
Softening point be 81%, elastic strength 97%, adhesive strength 0.65MPa.
Obtained emulsified asphalt is prepared into the ultra-thin wearing layer of pavement that thickness is about 1cm, skid number > 70BPN；
Water shutoff ability is significant, and section infiltration coefficient is 0.
As seen from the above embodiment, the present invention provides a kind of Camphor Tree Seeds cationic emulsifier and preparation method thereof and answer
With.The present invention carries out hydrotreating to camphor tree seed oil, obtains ten difatty acids of saturation；By ten difatty acids of the saturation 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；The amide intermediate is obtained into acyl with hcl reaction in dry toluene
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 using camphor tree seed oil as raw material and has prepared the raw material of cationic emulsifier, reduces
Cost, simultaneously because reduce the usage amount of industrial chemicals, it is environmentally protective, reduce the pollution to environment.In addition, by the present invention
The emulsified asphalt that the emulsifier of offer obtains 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 a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (2)
1. a kind of purposes of Camphor Tree Seeds cationic emulsifier as emulsified asphalt emulsifier,
The preparation of the Camphor Tree Seeds cationic emulsifier comprises the steps of:
(1) hydrotreating is carried out to camphor tree seed oil, obtains ten difatty acids of saturation；
(2) ten difatty acids of the saturation and N, N- dimethyl -1,3- propane diamine condensation is carried out to be acylated instead in mixed solution
It answers, obtains 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, obtains Camphor Tree Seeds cation
Emulsifier；
Volumetric concentration of the alkali metal hydroxide in mixed solution is 0.1~1%；
In the step (2), the mass ratio for being saturated ten difatty acids and N, N- dimethyl -1,3- propane diamine is 1:(1~3)；Institute
Stating volumetric concentration of ten difatty acids of saturation in mixed solution is 20~25%；
The Camphor Tree Seeds cationic emulsifier is used as emulsified asphalt emulsifier；
The temperature of the condensation acylation reaction is 75~85 DEG C；
The time of the condensation acylation reaction is 10~20 hours；
In terms of 1g amide intermediate, the flow velocity of the hydrogen chloride is 160~200mL/h；
In the step (4), the mass ratio of amide intermediate, amide intermediate hydrochloride and epichlorohydrin is (240~260):
(290~310): (90~110)；
The temperature of the heat treatment is 75~85 DEG C, and the time of the heat treatment is 3~10 hours.
2. application of the emulsified asphalt that Camphor Tree Seeds cationic emulsifier obtains as described in claim 1 as pavement abrasion layer.
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| 乳化沥青及其乳化剂的发展与应用;王长安 等，;《广州化学》;20060331;第31卷(第1期);第54-58页 * |
| 含酰胺基双子阳离子表面活性剂的合成与性能研究;陈凤生 等，;《日用化学工业》;20081031;第38卷(第5期);第286页 1.2 实验方法，第285页 左栏 倒数第2-3段，第287页右栏倒数第1段，第288页 3结论 * |
| 阳离子沥青乳化剂应用现状及研究进展;姚秀杰 等，;《广东化工》;20161231;第43卷(第334期);第136页 左栏 第1-2段，右栏第4段，第137页左栏 * |
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