CN107880070B - A kind of quaternary Hydroxypropyl phosphate ester sodium asphalt emulsifier and preparation method thereof - Google Patents
A kind of quaternary Hydroxypropyl phosphate ester sodium asphalt emulsifier and preparation method thereof Download PDFInfo
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- CN107880070B CN107880070B CN201711157807.6A CN201711157807A CN107880070B CN 107880070 B CN107880070 B CN 107880070B CN 201711157807 A CN201711157807 A CN 201711157807A CN 107880070 B CN107880070 B CN 107880070B
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- 239000010426 asphalt Substances 0.000 title claims abstract description 164
- 239000003995 emulsifying agent Substances 0.000 title claims abstract description 131
- 239000011734 sodium Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 69
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 68
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 title claims abstract description 66
- 150000002148 esters Chemical class 0.000 title claims abstract description 61
- HYCSHFLKPSMPGO-UHFFFAOYSA-N 3-hydroxypropyl dihydrogen phosphate Chemical group OCCCOP(O)(O)=O HYCSHFLKPSMPGO-UHFFFAOYSA-N 0.000 title claims abstract description 46
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 44
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 42
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims abstract description 27
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims abstract description 26
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 25
- 125000002091 cationic group Chemical group 0.000 claims abstract description 23
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims abstract description 14
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims abstract description 13
- 235000019799 monosodium phosphate Nutrition 0.000 claims abstract description 13
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims abstract description 13
- 239000007806 chemical reaction intermediate Substances 0.000 claims description 71
- 238000006243 chemical reaction Methods 0.000 claims description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 23
- 229910019142 PO4 Inorganic materials 0.000 claims description 22
- 239000000344 soap Substances 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 19
- 239000010452 phosphate Substances 0.000 claims description 15
- 238000004090 dissolution Methods 0.000 claims description 14
- 238000004945 emulsification Methods 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 150000001768 cations Chemical class 0.000 claims description 7
- 239000004593 Epoxy Substances 0.000 claims description 6
- -1 Hydroxypropyl phosphate ester Chemical class 0.000 claims description 6
- 239000000084 colloidal system Substances 0.000 claims description 5
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- VIRPUNZTLGQDDV-UHFFFAOYSA-N chloro propanoate Chemical compound CCC(=O)OCl VIRPUNZTLGQDDV-UHFFFAOYSA-N 0.000 claims 1
- 239000000543 intermediate Substances 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 47
- 238000010521 absorption reaction Methods 0.000 description 33
- 239000011295 pitch Substances 0.000 description 27
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 26
- 239000000243 solution Substances 0.000 description 20
- 238000005452 bending Methods 0.000 description 16
- 239000000047 product Substances 0.000 description 14
- 238000001514 detection method Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- 125000000129 anionic group Chemical group 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000003292 glue Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000006071 cream Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 3
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 3
- 229960003237 betaine Drugs 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- VUJQZKMFHLTXLX-UHFFFAOYSA-N OCCC[P] Chemical group OCCC[P] VUJQZKMFHLTXLX-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical group 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 2
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 2
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- LLQHSBBZNDXTIV-UHFFFAOYSA-N 6-[5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-4,5-dihydro-1,2-oxazol-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC1CC(=NO1)C1=CC2=C(NC(O2)=O)C=C1 LLQHSBBZNDXTIV-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 125000006414 CCl Chemical group ClC* 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- RFRIWRLHYDZFRS-UHFFFAOYSA-N [Na].[Na].[Na].P(O)(O)(O)=O Chemical compound [Na].[Na].[Na].P(O)(O)(O)=O RFRIWRLHYDZFRS-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012874 anionic emulsifier Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000001815 facial effect Effects 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000010200 validation analysis Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
-
- 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
-
- 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
- C08J2395/00—Bituminous materials, e.g. asphalt, tar or pitch
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of quaternary Hydroxypropyl phosphate ester sodium asphalt emulsifiers and preparation method thereof, which be prepared by the raw material of following mol ratio: octadecylamine, isopropanol, propylene oxide, epoxychloropropane, sodium dihydrogen phosphate molar ratio be 1mol:(4.00-9.00) mol:(4.00-4.20) mol:(1.00-1.15) mol:(1.50-1.73) mol.Alternatively, the molar ratio of octadecylamine, isopropanol, propylene oxide, epoxychloropropane, tertiary sodium phosphate, hydrochloric acid is 1mol:(4.00-9.00) mol:(4.00-4.20) mol:(1.00-1.15) mol:(1.30-1.50): (1.40-1.61) mol.The synthesis material of asphalt emulsifier of the invention is easy to get, production cost is low, simple process, does not need pyroreaction.The pitch of emulsifiable a variety of different models, the emulsified asphalt of preparation is fine and smooth uniformly, and storage stability is good, can prepare cationic emulsified asphalt.
Description
Technical field
The present invention relates to a kind of quaternary Hydroxypropyl phosphate ester sodium asphalt emulsifiers and preparation method thereof, belong to fining
Work technical field.
Background technique
Asphalt emulsifier is a seed type of surfactant, it has the fundamental characteristics of surfactant.Due to having
Lipophilic group and hydrophilic group enable it to be adsorbed on the mutually exclusive interface of pitch and water under the effect of the two groups, from
And reduce the interfacial tension between them.According to the difference of emulsifier hydrophilic group property, emulsifier is divided into anionic, cation
Type, amphoteric ion type, non-ionic etc..Wherein, amphoteric emulsifier carries negative ions charge simultaneously, its surface-active ion
Hydrophilic group not only there is anion part, but also there is cationic portion；Its structure is not only different from anionic emulsifier, but also has
Not in cationic emulsifier, therefore, there are many excellent performances, such as: (1) good emulsibility and dispersibility；(2) less toxic
Property；(3) resistance to hard water, calcium dispersibility are stronger, have good compatibility with the emulsifier of other kinds type.
In terms of the emulsification of pitch, although the asphalt emulsifier of numerous species exists in the prior art, China and America and Europe
Equal states still have gap: external asphalt emulsifier it is wide in variety, high-quality, produced there are many corresponding for different areas
Product, and domestic pitch is more single with emulsifier kind, effective component is low, poor to the adaptability of various pitches.It is especially related
The exploitation of both sexes asphalt emulsifier is later, and kind and quantity are all few, mainly includes betaines compound, imidazolines chemical combination
Object and amino acids etc..
It is newborn for amino and the simultaneous amphoteric of hydroxyl that United States Patent (USP) USP3342840 introduction has synthesized a kind of hydrophilic group
Agent, but the preparation cost of the emulsifier is higher.Chinese patent CN101712625A is related to a kind of amphoteric slow-breaking quick-setting asphalt cream
Agent synthetic method is reacted with polyamines using oleic acid and generates polyamide-polyamino, monoxone is then added, and asphalt emulsifier is made.It should
The shortcomings that method is to need pyroreaction when preparing.
Present inventor proposes a kind of preparation method of both sexes betaine type asphalt emulsifier in early-stage study, should
Emulsifier uses cocamidopropyl dimethyl tertiary amine for raw material, in alcohols solvent, obtains centre with epichlorohydrin reaction
Body；Continuation is reacted with dimethylamine agueous solution, sodium chloroacetate, obtains both sexes betaine type asphalt emulsifier.The asphalt emulsifier
Synthesis material is easy to get, production cost is low, simple process, does not need pyroreaction.But the both sexes betaine type asphalt emulsifier is
In split type.
Above-mentioned both sexes asphalt emulsifier and preparation method thereof generally existing deficiency is: prepare the cost of material of emulsifier compared with
Height, source are restricted, and when preparation needs pyroreaction, higher to productive experiment equipment requirement.
Therefore, it is necessary to new both sexes asphalt emulsifier be developed, to enrich the type of both sexes asphalt emulsifier, so that pitch
The cost of emulsifier is cheaper, technique is simpler, meets the application requirement of road construction and pavement preservation.
Summary of the invention
For the deficiencies in the prior art, low, simple process that the purpose of the present invention is to provide a kind of production costs,
The quaternary Hydroxypropyl phosphate ester sodium asphalt emulsifier and preparation method thereof of pyroreaction is not needed.
To achieve the above object, the present invention adopts the following technical scheme:
The first aspect of the invention provides a kind of quaternary Hydroxypropyl phosphate ester sodium asphalt emulsifier, molecule knot
Structure general formula are as follows:
Wherein, when x=1, y=1；When x=0, y=2；
That is, x=1, y=1, molecular structural formula are as follows:
That is, x=0, y=2, molecular structural formula are as follows:
The quaternary Hydroxypropyl phosphate ester sodium asphalt emulsifier especially, is being prepared in the application for preparing emulsified asphalt
The application in type cationic emulsified bitumen is split fastly.
The second aspect of the invention provides a kind of preparation side of quaternary Hydroxypropyl phosphate ester sodium asphalt emulsifier
Method, comprising the following steps:
(1) by octadecylamine, isopropanol and propylene oxide hybrid reaction, reaction intermediate I, the reaction intermediate I are obtained
Structural formula be
C18H37N(CH2CH(CH3)OCH2CH(OH)CH3)2；
(2) sodium dihydrogen phosphate is soluble in water, it is heated to certain temperature, then be gradually added into epoxychloropropane, hybrid reaction,
Reaction intermediate II is obtained, reaction intermediate II is 3- chlorine-2-hydroxyl propyl phosphate sodium
(3) reaction intermediate II is added in reaction intermediate I, hybrid reaction to get arrive quaternary hydroxypropyl phosphorus
Acid esters sodium asphalt emulsifier；
Or, the following steps are included:
(1) by octadecylamine, isopropanol and propylene oxide hybrid reaction, reaction intermediate I, the reaction intermediate I are obtained
Structural formula be
C18H37N(CH2CH(CH3)OCH2CH(OH)CH3)2；
(2) tertiary sodium phosphate is soluble in water, it is heated to certain temperature, then be gradually added into epoxychloropropane, hybrid reaction obtains
It is phosphate epoxypropyl ester sodium to reaction intermediate III, reaction intermediate III
(3) reaction intermediate III is added in reaction intermediate I, then is gradually added into hydrochloric acid, hybrid reaction is to get arriving
Quaternary Hydroxypropyl phosphate ester sodium asphalt emulsifier.
The third aspect of the invention provides a kind of preparation method of cationic emulsified bitumen, includes the following steps: pitch
The dosage of emulsifier is the 1.0-3.0% of the emulsified asphalt gross mass of preparation, adds water to be configured to above-mentioned asphalt emulsifier water-soluble
Liquid adjusts pH value to 2-3 with technical hydrochloric acid, is heated to 60-70 DEG C, soap lye is made；By the pitch and emulsifier soap lye after heating
Cationic emulsified bitumen is prepared by colloid mill emulsification.
The cationic emulsified bitumen that above-mentioned preparation method is prepared.
In above-mentioned preparation method, after adjusting pH value with technical hydrochloric acid, above two asphalt emulsifier molecular structure becomes phase
Same molecular structure serves identical.
Alternatively, providing a kind of preparation method of anionic emulsified bitumen, include the following steps: that the dosage of asphalt emulsifier is
Above-mentioned asphalt emulsifier is added water to be configured to aqueous solution by the 1.0-3.0% of the emulsified asphalt gross mass of preparation, with sodium hydroxide tune
PH value is saved to 10-11,60-70 DEG C is heated to, soap lye is made；By after heating pitch and emulsifier soap lye pass through colloid mill emulsify
Prepare anionic emulsified bitumen.
The anionic emulsified bitumen that above-mentioned preparation method is prepared.
In above-mentioned preparation method, after adjusting pH value with sodium hydroxide, above two asphalt emulsifier molecular structure becomes phase
Same molecular structure serves identical.
Compared with prior art, the beneficial effect of technical solution of the present invention is:
(1) by the way that propylene oxide is added in raw material of the invention, so that the asphalt emulsification agent molecule that the present invention is prepared
Hydrophily it is larger；The addition of epoxychloropropane and sodium dihydrogen phosphate (or tertiary sodium phosphate), makes the asphalt emulsifier being prepared
Molecule has quaternary Hydroxypropyl phosphate ester Sodium chemistry structure, enhances the charge density of asphalt emulsification agent molecule.
The hydrophilic group contained in asphalt emulsifier structural formula of the invention is more, hydroxyl, phosphate and quaternary ammonium salt, so that boundary
Facial mask, hydration layer and interface charge layer all enhance accordingly, improve emulsion intercalation method.
(2) present invention is using specific raw material propylene oxide, octadecylamine, epoxychloropropane and sodium dihydrogen phosphate (or phosphoric acid
Trisodium), the asphalt emulsifier with certain HLB value is generated, is dripped using quaternary Hydroxypropyl phosphate ester sodium prepared by the present invention
Green emulsifier have good emulsifiability, the performance indexes for the emulsified asphalt being prepared is excellent, it is emulsifiable it is a variety of not
With the pitch of model, the emulsified asphalt of preparation is fine and smooth uniformly, have it is good gather materials wrap up in attached property and storage stability.Suitable for public affairs
The spread of road priming oil or sticking layer oil, and be used for crushed stone sealing, screening seal coat, mist sealing and reparation slight check crack in road surface etc.,
With the characteristic for splitting asphalt emulsifier fastly.
(3) the raw material octadecylamine of quaternary Hydroxypropyl phosphate ester sodium asphalt emulsifier of the invention is relative to current sun
Raw material used in ionic asphalt emulsifier is cheap, from a wealth of sources, and asphalt emulsifier production cost is low.
(4) amide groups amine emulsifier reaction temperature general control is and of the invention at 140~180 DEG C in the prior art
The preparation method simple process of quaternary Hydroxypropyl phosphate ester sodium asphalt emulsifier does not need pyroreaction, reduces energy consumption.
(5) there are anionic group and cation group, both sexes simultaneously in asphalt emulsifier molecular structure of the present invention
Emulsifier is applicable to different environment, the feature of cationic surface active agent is presented in an acidic solution, in alkaline solution
The middle feature that anionic surfactant is presented.
Specific embodiment
It is noted that described further below be all exemplary, it is intended to provide further instruction to the present invention.Unless another
It indicates, all technical and scientific terms used herein has usual with general technical staff of the technical field of the invention
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root
According to exemplary embodiments of the present invention.As used herein, unless the context clearly indicates otherwise, otherwise singular
Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, component and/or their combination.
Used raw material, reagent are conventional chemical product in the embodiment of the present invention, can be commercially available by market.
In order to enrich the type of both sexes asphalt emulsifier, the present invention provides a kind of quaternary Hydroxypropyl phosphate ester sodium pitch
Emulsifier, general formula of molecular structure are as follows:
Wherein, when x=1, y=1；When x=0, y=2；
That is, x=1, y=1, molecular structural formula are as follows:
That is, x=0, y=2, molecular structural formula are as follows:
The structure for analyzing the quaternary Hydroxypropyl phosphate ester sodium asphalt emulsifier, by hydroxyl, phosphate and quaternary ammonium salt
Hydrophilic radical is effectively combined in the form of certain group, in addition suitable carbon-chain structure and other lipophilic groups, jointly
Form this new structural asphalt emulsifier.
For the above asphalt emulsifier, the present invention also provides its preparation methods, comprising the following steps:
(1) by octadecylamine, isopropanol and propylene oxide hybrid reaction, reaction intermediate I, the reaction intermediate I are obtained
Structural formula be
C18H37N(CH2CH(CH3)OCH2CH(OH)CH3)2；
(2) sodium dihydrogen phosphate is soluble in water, it is heated to certain temperature, then be gradually added into epoxychloropropane, hybrid reaction,
Reaction intermediate II is obtained, reaction intermediate II is 3- chlorine-2-hydroxyl propyl phosphate sodium
(3) reaction intermediate II is added in reaction intermediate I, hybrid reaction to get arrive quaternary hydroxypropyl phosphorus
Acid esters sodium asphalt emulsifier；
Or, the following steps are included:
(1) by octadecylamine, isopropanol and propylene oxide hybrid reaction, reaction intermediate I, the reaction intermediate I are obtained
Structural formula be
C18H37N(CH2CH(CH3)OCH2CH(OH)CH3)2；
(2) tertiary sodium phosphate is soluble in water, it is heated to certain temperature, then be gradually added into epoxychloropropane, hybrid reaction obtains
It is phosphate epoxypropyl ester sodium to reaction intermediate III, reaction intermediate III
(3) reaction intermediate III is added in reaction intermediate I, then is gradually added into hydrochloric acid, hybrid reaction is to get arriving
Quaternary Hydroxypropyl phosphate ester sodium asphalt emulsifier.
In currently preferred technical solution, the reaction intermediate II (3- chlorine-2-hydroxyl propyl phosphate sodium)
Preparation method, it is preferred that the temperature of reaction is 75-95 DEG C, and further preferably 80-90 DEG C, the time of reaction is 5-8h.
In currently preferred technical solution, the preparation side of the reaction intermediate III (phosphate epoxypropyl ester sodium)
Method, it is preferred that the temperature of reaction is 42 DEG C, and the time of reaction is 5h.During the experiment inventors have found that in higher reaction temperature
Under the conditions of degree, since side reaction is more, it cannot get reaction intermediate III (phosphate epoxypropyl ester sodium) aqueous solution.
In some preferred technical solutions of the present invention, octadecylamine, isopropanol, propylene oxide, epoxychloropropane, di(2-ethylhexyl)phosphate
The molar ratio of hydrogen sodium is 1mol:(4.00-9.00) mol:(4.00-4.20) mol:(1.00-1.15) mol:(1.50-1.73)
mol。
In some preferred technical solutions of the present invention, octadecylamine, isopropanol, propylene oxide, epoxychloropropane, tricresyl phosphate
Sodium, hydrochloric acid molar ratio be 1mol:(4.00-9.00) mol:(4.00-4.20) mol:(1.00-1.15) mol:(1.30-
1.50): (1.40-1.61) mol.
By lot of experiment validation and analysis, each raw material of above-mentioned molar ratio makes the quaternary ammonium salt of the invention being prepared
The performance of type Hydroxypropyl phosphate ester sodium asphalt emulsifier is more satisfactory, and the raw material of inappropriate proportion relation cannot form quaternary
Hydroxypropyl phosphate ester sodium asphalt emulsifier.
In some preferred technical solutions of the present invention, in step (1), the temperature of reaction is 60-80 DEG C, preferably 65-
75 DEG C, the time of reaction is 2-4h.
In some preferred technical solutions of the present invention, in step (3), the temperature of reaction is 60-80 DEG C, preferably 65-
75 DEG C, the time of reaction is 3-6h.
In some preferred technical solutions of the invention, the system of the quaternary Hydroxypropyl phosphate ester sodium asphalt emulsifier
Preparation Method specifically comprises the following steps:
(1) octadecylamine is added in reaction vessel, isopropanol, heating stirring dissolution is added, then epoxy third is added portionwise
Alkane after addition, is stirred to react 2-4h at 60-80 DEG C, obtains reaction intermediate I；
(2) sodium dihydrogen phosphate is added in another reaction vessel, adds water, heating stirring dissolution, then epoxy is added portionwise
Chloropropane after addition, is stirred to react 5-8h at 75-95 DEG C, obtains reaction intermediate II (3- chlorine-2-hydroxyl propyl phosphoric acid
Ester sodium)；
(3) reaction intermediate II is added portionwise in reaction intermediate I, 60-80 DEG C of reaction 3-6h to get arrive quaternary ammonium
Salt form Hydroxypropyl phosphate ester sodium asphalt emulsifier；
Or, specifically comprising the following steps:
(1) octadecylamine is added in reaction vessel, isopropanol, heating stirring dissolution is added, then epoxy third is added portionwise
Alkane after addition, is stirred to react 2-4h at 60-80 DEG C, obtains reaction intermediate I；
(2) tertiary sodium phosphate is added in another reaction vessel, adds water, heating stirring dissolution, then epoxy chlorine is added portionwise
Propane after addition, is stirred to react 5h at 42 DEG C, obtains reaction intermediate III (phosphate epoxypropyl ester sodium)；
(3) reaction intermediate III is added in reaction intermediate I, then hydrochloric acid is added portionwise, in 60-80 DEG C of reaction 3-
6h to get arrive quaternary Hydroxypropyl phosphate ester sodium asphalt emulsifier.
The quaternary hydroxypropyl that above-mentioned quaternary Hydroxypropyl phosphate ester sodium asphalt emulsifier or above-mentioned preparation method obtain
Base sodium phosphate asphalt emulsifier is preparing the application in emulsified asphalt, especially, splits type cationic emulsified bitumen fastly in preparation
In application.
Reaction raw materials of the present invention using propylene oxide as asphalt emulsifier, pass through in the molecular structure of asphalt emulsifier
Propylene oxide is added and introduces hydroxyl, increases the hydrophily of asphalt emulsifier and the compatibility of emulsifier and pitch.Separately
Outside, carbon chain lengths are comprehensively considered for the HLB value (hydrophilic/lipophilic balance value) and CMC (critical micelle concentration) of asphalt emulsifier
Influence, select using octadecylamine, epoxychloropropane and sodium dihydrogen phosphate (or tertiary sodium phosphate) as reaction raw material, make preparation
The HLB value of asphalt emulsifier improves the emulsifiability to pitch within optimum range.
For the quaternary Hydroxypropyl phosphate ester sodium asphalt emulsifier in the present invention, the present invention also provides a kind of cations
The preparation method of emulsified asphalt includes the following steps: that the dosage of asphalt emulsifier is the 1.0- of the emulsified asphalt gross mass of preparation
3.0%, add water to be configured to aqueous solution above-mentioned asphalt emulsifier, with technical hydrochloric acid adjusting pH value to 2-3, is heated to 60-70 DEG C,
Soap lye is made；By after heating pitch and emulsifier soap lye by colloid mill emulsification prepare cationic emulsified bitumen.
The cationic emulsified bitumen that above-mentioned preparation method is prepared.
For the quaternary Hydroxypropyl phosphate ester sodium asphalt emulsifier in the present invention, the present invention also provides a kind of anion
The preparation method of emulsified asphalt includes the following steps: that the dosage of asphalt emulsifier is the 1.0- of the emulsified asphalt gross mass of preparation
3.0%, add water to be configured to aqueous solution the asphalt emulsifier that above-mentioned asphalt emulsifier or above-mentioned preparation method obtain, uses hydroxide
Sodium adjusts pH value to 10-11, is heated to 60-70 DEG C, soap lye is made；By after heating pitch and emulsifier soap lye pass through colloid mill
Anionic emulsified bitumen is prepared in emulsification.
The anionic emulsified bitumen that above-mentioned preparation method is prepared.
In order to enable those skilled in the art can clearly understand the technical solution of the application, below with reference to tool
The technical solution of the application is described in detail in the embodiment and comparative example of body.
Embodiment 1
(1) preparation of quaternary Hydroxypropyl phosphate ester sodium asphalt emulsifier:
1) 269.5g octadecylamine, 260g isopropanol, heating stirring dissolution are added in the reactor.Then it is gradually added into
238.1g propylene oxide, 70 DEG C are stirred to react 3h.
2) 245.7g sodium dihydrogen phosphate (NaH is added in another reactor2PO4·2H2O) and 483g water, stirring and dissolving,
It is heated to 85 DEG C.97.1g epoxychloropropane is added dropwise again, 85 DEG C are stirred to react 7.5h, obtain 3- chlorine-2-hydroxyl propyl phosphate sodium
Aqueous solution.
The above-mentioned intermediate product of synthesis carries out FTIR detection after recrystallizing separating-purifying, as a result as follows: 3445cm-1For O-
The stretching vibration absworption peak of H, 1635cm-1For C-O asymmetric stretching vibration absorption peak, 1297cm-1It is inhaled for the stretching vibration of P=O
Receive peak, 1093cm-1For the stretching vibration absworption peak of P-O-R, 921cm-1For P-OH vibration absorption peak, 665cm-1For C-Cl bending
Vibration absorption peak, 538cm-1For O-H out-of-plane bending vibration absorption peak.
3) 3- chlorine-2-hydroxyl propyl phosphate sodium water solution prepared by step 2) is added drop-wise to above-mentioned steps 1) synthetic product
In, 65 DEG C are stirred to react 4h.Quaternary Hydroxypropyl phosphate ester sodium asphalt emulsifier is obtained, emulsified asphalt test is given over to.
Synthetic product carries out FTIR detection after recrystallizing separating-purifying, as a result as follows: 3432cm-1For the flexible vibration of O-H
Dynamic absorption peak, 2916cm-1For the asymmetric stretching vibration absworption peak of methylene, 2846cm-1For the symmetrical stretching vibration of methylene
Receive peak, 1472cm-1It is vibrated for the asymmetric curvature of methylene, 1389cm-1It is vibrated for the asymmetric curvature of methyl, 1236cm-1For
The stretching vibration absworption peak of P=O, 1081cm-1For the stretching vibration absworption peak of P-O-R, 964cm-1For O-H out-of-plane bending vibration
Absorption peak, 719cm-1For methylene rocking vibration absorption peak, 545cm-1For O-H in-plane bending vibration absorption peak.
Reaction equation is as follows:
(2) preparation of emulsified asphalt:
AH-90# pitch 300g is taken, is heated to 125 DEG C, 12.5g asphalt emulsifier manufactured in the present embodiment is added to
In 200g water, pH value is adjusted to 2-3 with technical hydrochloric acid, 65 DEG C is heated to, soap lye is made.Pitch and emulsifier soap lye are passed through into glue
Cationic emulsified asphalt is prepared in body mill emulsification.
(3) emulsified asphalt performance detection:
Emulsified asphalt obtained by Chinese transportation portion work out cationic emulsified bitumen professional standard (JTJ052-2000) into
Row detection, as a result as follows: emulsified asphalt manufactured in the present embodiment is uniform, fine and smooth, bitumen content 59%, and surplus is on sieve
0.03%, area is wrapped greater than 2/3 with mineral aggregate, and charge is cation；It is mixed and stirred using material is mixed and stirred, can be 2 seconds the mixing time.
The asphalt emulsion for showing emulsifier preparation is to split type cationic emulsified bitumen fastly, and asphalt emulsifier is to split type fastly.
Embodiment 2
(1) preparation of quaternary Hydroxypropyl phosphate ester sodium asphalt emulsifier:
1) 269.5g octadecylamine, 260g isopropanol, heating stirring dissolution are added in the reactor.Then it is gradually added into
238.1g propylene oxide, 70 DEG C are stirred to react 3h.
2) 518.9g tertiary sodium phosphate (Na is added in another reactor3PO4·12H2O) add with 672g water, stirring and dissolving
Heat is to 42 DEG C.97.1g epoxychloropropane is added dropwise again, 42 DEG C are stirred to react 5h, obtain phosphate epoxypropyl ester sodium water solution.
The above-mentioned intermediate product of synthesis carries out FTIR detection after recrystallizing separating-purifying, as a result as follows: 3015cm-1For ring
Oxygen groups C-H stretching vibration absworption peak, 1673cm-1For C-O asymmetric stretching vibration absorption peak, 1443cm-1For the non-of methylene
Symmetric curvature vibration, 1360cm-1For the stretching vibration absworption peak of P=O, 1023cm-1For the stretching vibration absworption peak of P-O-R,
933cm-1For epoxy group vibration absorption peak, 736cm-1For C-H out-of-plane bending vibration absorption peak.
3) phosphate epoxypropyl ester sodium water solution prepared by step 2) is added drop-wise to above-mentioned steps 1) in synthetic product, then drip
Add 170.1g hydrochloric acid (30%), 75 DEG C are stirred to react 3h.Quaternary Hydroxypropyl phosphate ester sodium asphalt emulsifier is obtained, cream is given over to
Change asphalt test.
Synthetic product carries out FTIR detection after recrystallizing separating-purifying, as a result as follows: 3427cm-1For the flexible vibration of O-H
Dynamic absorption peak, 2923cm-1For the asymmetric stretching vibration absworption peak of methylene, 2847cm-1For the symmetrical stretching vibration of methylene
Receive peak, 1470cm-1It is vibrated for the asymmetric curvature of methylene, 1399cm-1It is vibrated for the asymmetric curvature of methyl, 1277cm-1For
The stretching vibration absworption peak of P=O, 1068cm-1For the stretching vibration absworption peak of P-O-R, 972cm-1For O-H out-of-plane bending vibration
Absorption peak, 723cm-1For methylene rocking vibration absorption peak, 544cm-1For O-H in-plane bending vibration absorption peak.
Reaction equation is as follows:
(2) preparation of emulsified asphalt:
AH-70# pitch 300g is taken, is heated to 125 DEG C, 12.5g asphalt emulsifier manufactured in the present embodiment is added to
In 200g water, pH value is adjusted to 2-3 with technical hydrochloric acid, 65 DEG C is heated to, soap lye is made.Pitch and emulsifier soap lye are passed through into glue
Cationic emulsified asphalt is prepared in body mill emulsification.
(3) emulsified asphalt performance detection:
Detection method is the same as embodiment 1, testing result are as follows: emulsified asphalt is uniform, fine and smooth, bitumen content 57%, remains on sieve
Surplus is 0.03%, wraps area greater than 2/3 with mineral aggregate, charge is cation；It is mixed and stirred using material is mixed and stirred, it can the mixing time
It is 3 seconds.The asphalt emulsion for showing emulsifier preparation is to split type cationic emulsified bitumen fastly, and asphalt emulsifier is to split type fastly.
Comparative example 1
(1) preparation of quaternary Hydroxypropyl phosphate ester sodium asphalt emulsifier:
1) 269.5g octadecylamine, 260g isopropanol, heating stirring dissolution are added in the reactor.Then it is gradually added into
122.0g propylene oxide, 70 DEG C are stirred to react 3h.
2) 245.7g sodium dihydrogen phosphate (NaH is added in another reactor2PO4·2H2O) and 483g water, stirring and dissolving,
It is heated to 85 DEG C.97.1g epoxychloropropane is added dropwise again, 85 DEG C are stirred to react 7.5h, obtain 3- chlorine-2-hydroxyl propyl phosphate sodium
Aqueous solution.
3) 3- chlorine-2-hydroxyl propyl phosphate sodium water solution prepared by step 2) is added drop-wise to above-mentioned steps 1) synthetic product
In, 65 DEG C are stirred to react 4h.Quaternary Hydroxypropyl phosphate ester sodium asphalt emulsifier is obtained, emulsified asphalt test is given over to.
Synthetic product carries out FTIR detection after recrystallizing separating-purifying, as a result as follows: 3420cm-1For the flexible vibration of O-H
Dynamic absorption peak, 2917cm-1For the asymmetric stretching vibration absworption peak of methylene, 2847cm-1For the symmetrical stretching vibration of methylene
Receive peak, 1475cm-1It is vibrated for the asymmetric curvature of methylene, 1399cm-1It is vibrated for the asymmetric curvature of methyl, 1240cm-1For
The stretching vibration absworption peak of P=O, 1092cm-1For the stretching vibration absworption peak of P-O-R, 959cm-1For O-H out-of-plane bending vibration
Absorption peak, 723cm-1For methylene rocking vibration absorption peak, 538cm-1For O-H in-plane bending vibration absorption peak.
(2) preparation of emulsified asphalt:
AH-90# pitch 300g is taken, is heated to 125 DEG C, 12.5g asphalt emulsifier manufactured in the present embodiment is added to
In 200g water, pH value is adjusted to 2-3 with technical hydrochloric acid, 65 DEG C is heated to, soap lye is made.Pitch and emulsifier soap lye are passed through into glue
Cationic emulsified asphalt is prepared in body mill emulsification.As a result: cannot emulsify.
Comparative example 2
(1) preparation of quaternary Hydroxypropyl phosphate ester sodium asphalt emulsifier:
1) 269.5g octadecylamine, 260g isopropanol, heating stirring dissolution are added in the reactor.Then it is gradually added into
354.3g propylene oxide, 70 DEG C are stirred to react 3h.
2) 245.7g sodium dihydrogen phosphate (NaH is added in another reactor2PO4·2H2O) and 483g water, stirring and dissolving,
It is heated to 85 DEG C.97.1g epoxychloropropane is added dropwise again, 85 DEG C are stirred to react 7.5h, obtain 3- chlorine-2-hydroxyl propyl phosphate sodium
Aqueous solution.
3) 3- chlorine-2-hydroxyl propyl phosphate sodium water solution prepared by step 2) is added drop-wise to above-mentioned steps 1) synthetic product
In, 65 DEG C are stirred to react 4h.Quaternary Hydroxypropyl phosphate ester sodium asphalt emulsifier is obtained, emulsified asphalt test is given over to.
Synthetic product carries out FTIR detection after recrystallizing separating-purifying, as a result as follows: 3408cm-1For the flexible vibration of O-H
Dynamic absorption peak, 2910cm-1For the asymmetric stretching vibration absworption peak of methylene, 2847cm-1For the symmetrical stretching vibration of methylene
Receive peak, 1470cm-1It is vibrated for the asymmetric curvature of methylene, 1393cm-1It is vibrated for the asymmetric curvature of methyl, 1240cm-1For
The stretching vibration absworption peak of P=O, 1080cm-1For the stretching vibration absworption peak of P-O-R, 959cm-1For O-H out-of-plane bending vibration
Absorption peak, 717cm-1For methylene rocking vibration absorption peak, 545cm-1For O-H in-plane bending vibration absorption peak.
(2) preparation of emulsified asphalt:
AH-90# pitch 300g is taken, is heated to 125 DEG C, 12.5g asphalt emulsifier manufactured in the present embodiment is added to
In 200g water, pH value is adjusted to 2-3 with technical hydrochloric acid, 65 DEG C is heated to, soap lye is made.Pitch and emulsifier soap lye are passed through into glue
Cationic emulsified asphalt is prepared in body mill emulsification.As a result: cannot emulsify.
Comparative example 3
(1) preparation of quaternary Hydroxypropyl phosphate ester sodium asphalt emulsifier:
1) 269.5g octadecylamine, 260g isopropanol, heating stirring dissolution are added in the reactor.Then it is gradually added into
122.0g propylene oxide, 70 DEG C are stirred to react 3h.
2) 518.9g tertiary sodium phosphate (Na is added in another reactor3PO4·12H2O) add with 672g water, stirring and dissolving
Heat is to 42 DEG C.97.1g epoxychloropropane is added dropwise again, 42 DEG C are stirred to react 5h, obtain phosphate epoxypropyl ester sodium water solution.
3) phosphate epoxypropyl ester sodium water solution prepared by step 2) is added drop-wise to above-mentioned steps 1) in synthetic product, then drip
Add 170.1g hydrochloric acid (30%), 75 DEG C are stirred to react 3h.Quaternary Hydroxypropyl phosphate ester sodium asphalt emulsifier is obtained, cream is given over to
Change asphalt test.
Synthetic product carries out FTIR detection after recrystallizing separating-purifying, as a result as follows: 3420cm-1For the flexible vibration of O-H
Dynamic absorption peak, 2917cm-1For the asymmetric stretching vibration absworption peak of methylene, 2847cm-1For the symmetrical stretching vibration of methylene
Receive peak, 1475cm-1It is vibrated for the asymmetric curvature of methylene, 1399cm-1It is vibrated for the asymmetric curvature of methyl, 1271cm-1For
The stretching vibration absworption peak of P=O, 1074cm-1For the stretching vibration absworption peak of P-O-R, 965cm-1For O-H out-of-plane bending vibration
Absorption peak, 716cm-1For methylene rocking vibration absorption peak, 538cm-1For O-H in-plane bending vibration absorption peak.
Reaction equation is as follows:
(2) preparation of emulsified asphalt:
AH-70# pitch 300g is taken, is heated to 125 DEG C, 12.5g asphalt emulsifier manufactured in the present embodiment is added to
In 200g water, pH value is adjusted to 2-3 with technical hydrochloric acid, 65 DEG C is heated to, soap lye is made.Pitch and emulsifier soap lye are passed through into glue
Cationic emulsified asphalt is prepared in body mill emulsification.As a result: cannot emulsify.
Comparative example 4
(1) preparation of quaternary Hydroxypropyl phosphate ester sodium asphalt emulsifier:
1) 269.5g octadecylamine, 260g isopropanol, heating stirring dissolution are added in the reactor.Then it is gradually added into
354.3g propylene oxide, 70 DEG C are stirred to react 3h.
2) 518.9g tertiary sodium phosphate (Na is added in another reactor3PO4·12H2O) add with 672g water, stirring and dissolving
Heat is to 42 DEG C.97.1g epoxychloropropane is added dropwise again, 42 DEG C are stirred to react 5h, obtain phosphate epoxypropyl ester sodium water solution.
3) phosphate epoxypropyl ester sodium water solution prepared by step 2) is added drop-wise to above-mentioned steps 1) in synthetic product, then drip
Add 170.1g hydrochloric acid (30%), 75 DEG C are stirred to react 3h.Quaternary Hydroxypropyl phosphate ester sodium asphalt emulsifier is obtained, cream is given over to
Change asphalt test.
Synthetic product carries out FTIR detection after recrystallizing separating-purifying, as a result as follows: 3423cm-1For the flexible vibration of O-H
Dynamic absorption peak, 2918cm-1For the asymmetric stretching vibration absworption peak of methylene, 2842cm-1For the symmetrical stretching vibration of methylene
Receive peak, 1471cm-1It is vibrated for the asymmetric curvature of methylene, 1285cm-1For the stretching vibration absworption peak of P=O, 1069cm-1For
The stretching vibration absworption peak of P-O-R, 967cm-1For O-H out-of-plane bending vibration absorption peak, 718cm-1To wave vibration in methylene basal plane
Dynamic absorption peak, 534cm-1For O-H in-plane bending vibration absorption peak.
Reaction equation is as follows:
(2) preparation of emulsified asphalt:
AH-70# pitch 300g is taken, is heated to 125 DEG C, 12.5g asphalt emulsifier manufactured in the present embodiment is added to
In 200g water, pH value is adjusted to 2-3 with technical hydrochloric acid, 65 DEG C is heated to, soap lye is made.Pitch and emulsifier soap lye are passed through into glue
Cationic emulsified asphalt is prepared in body mill emulsification.As a result: cannot emulsify.
Comparative example 5
(1) preparation of reaction intermediate:
465.6g disodium hydrogen phosphate (Na is added in the reactor2HPO4·12H2O it) is heated to 460g water, stirring and dissolving
42℃.92.45g epoxychloropropane is added dropwise again, 42 DEG C are stirred to react 5h.Phenomenon: with the presence of oily mutually (unreacted epoxy chloropropionate
Alkane), it does not react, cannot get corresponding reaction intermediate.
Comparative example 6
(1) preparation of reaction intermediate:
162.6g sodium bisulfate (NaHSO is added in the reactor4·H2O) and 392.7g water, stirring and dissolving are heated to 75
℃.98.9g epoxychloropropane is added dropwise again, 75 DEG C are stirred to react 3.5h.It cannot get corresponding reaction intermediate (3- chlorine-2-hydroxyl
Propyl sodium sulphate) aqueous solution.
Comparative example 7
(1) preparation of reaction intermediate:
518.9g tertiary sodium phosphate (Na is added in the reactor3PO4·12H2O) and 672g water, stirring and dissolving are heated to 70
℃.97.1g epoxychloropropane is added dropwise again, 70 DEG C are stirred to react 5h.
The above-mentioned intermediate product of synthesis carries out FTIR detection after recrystallizing separating-purifying, as a result as follows: 3418cm-1For O-
The stretching vibration absworption peak of H, 1654cm-1For C-O asymmetric stretching vibration absorption peak, 990cm-1It is absorbed for the bending vibration of C-H
Peak, 670cm-1For methylene rocking vibration absorption peak.It can be seen that: when reaction temperature is higher, it is greater than equal to 70 DEG C, by
It is more in side reaction, it cannot get reaction intermediate III (phosphate epoxypropyl ester sodium) aqueous solution.
Conclusion 1: available based on above embodiments and comparative example, the present invention is to filter out excellent asphalt emulsifier
Starting point reasonably selects reaction raw materials, asphalt emulsifier and cationic emulsified bitumen is prepared.Present invention selection
Specific raw material (propylene oxide and octadecylamine), so that specific reaction intermediate I is formed, in reaction intermediate I and reaction
Mesosome II (or reaction intermediate III), which is reacted, can just obtain new structural quaternary Hydroxypropyl phosphate ester sodium pitch cream
Agent, in process of experimental, inventors have surprisingly discovered that the asphalt emulsifier has excellent emulsifiability, and comparative example
Emulsified asphalt is unable to by the emulsifier that other reaction intermediate I are obtained in 1~4.
Conclusion 2: it is available based on above embodiments and comparative example, reaction raw materials are reasonably selected and are reacted with item
Corresponding reaction intermediate can be just prepared in the control of part.The specific raw material sodium dihydrogen phosphate of present invention selection (or tricresyl phosphate
Sodium) and epoxychloropropane hybrid reaction, to form specific reaction intermediate II (or reaction intermediate III), and further
New structural quaternary Hydroxypropyl phosphate ester sodium asphalt emulsifier can just be obtained by being reacted, in process of experimental,
Inventors have surprisingly discovered that the asphalt emulsifier has excellent emulsifiability.And by other raw material (phosphoric acid in comparative example 5-6
Disodium hydrogen or sodium bisulfate) with epoxychloropropane hybrid reaction, cannot get corresponding reaction intermediate, also cannot further into
Row reaction obtains new structural quaternary Hydroxypropyl phosphate ester sodium asphalt emulsifier.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (13)
1. a kind of quaternary Hydroxypropyl phosphate ester sodium asphalt emulsifier, characterized in that the quaternary Hydroxypropyl phosphate ester
Sodium asphalt emulsifier general formula of molecular structure are as follows:
Wherein, when x=1, y=1；When x=0, y=2；
That is, x=1, y=1, molecular structural formula are as follows:
That is, x=0, y=2, molecular structural formula are as follows:
2. the preparation method of quaternary Hydroxypropyl phosphate ester sodium asphalt emulsifier described in claim 1, characterized in that including
Following steps:
(1) by octadecylamine, isopropanol and propylene oxide hybrid reaction, reaction intermediate I, the knot of the reaction intermediate I are obtained
Structure formula is
C18H37N(CH2CH(CH3)OCH2CH(OH)CH3)2；
(2) sodium dihydrogen phosphate is soluble in water, it is heated to certain temperature, then be gradually added into epoxychloropropane, hybrid reaction obtains
Reaction intermediate II, reaction intermediate II are 3- chlorine-2-hydroxyl propyl phosphate sodium
(3) reaction intermediate II is added in reaction intermediate I, hybrid reaction to get arrive quaternary Hydroxypropyl phosphate ester
Sodium asphalt emulsifier；
Or, the following steps are included:
(1) by octadecylamine, isopropanol and propylene oxide hybrid reaction, reaction intermediate I, the knot of the reaction intermediate I are obtained
Structure formula is
C18H37N(CH2CH(CH3)OCH2CH(OH)CH3)2；
(2) tertiary sodium phosphate is soluble in water, it is heated to certain temperature, then be gradually added into epoxychloropropane, hybrid reaction obtains anti-
Intermediate III is answered, reaction intermediate III is phosphate epoxypropyl ester sodium
(3) reaction intermediate III is added in reaction intermediate I, then is gradually added into hydrochloric acid, hybrid reaction to get arrive quaternary ammonium
Salt form Hydroxypropyl phosphate ester sodium asphalt emulsifier.
3. preparation method as claimed in claim 2, characterized in that the preparation method of the reaction intermediate II, the temperature of reaction
Degree is 75-95 DEG C, and the time of reaction is 5-8h；
The preparation method of the reaction intermediate III, the temperature of reaction are 42 DEG C, and the time of reaction is 5h.
4. preparation method as claimed in claim 3, characterized in that the preparation method of the reaction intermediate II, the temperature of reaction
Degree is 80-90 DEG C.
5. preparation method as claimed in claim 2, characterized in that octadecylamine, isopropanol, propylene oxide, epoxychloropropane, phosphorus
The molar ratio of acid dihydride sodium is 1mol:(4.00-9.00) mol:(4.00-4.20) mol:(1.00-1.15) mol:(1.50-
1.73)mol；Octadecylamine, isopropanol, propylene oxide, epoxychloropropane, tertiary sodium phosphate, hydrochloric acid molar ratio be 1mol:(4.00-
9.00) mol:(4.00-4.20) mol:(1.00-1.15) mol:(1.30-1.50): (1.40-1.61) mol.
6. preparation method as claimed in claim 2, characterized in that in step (1), the temperature of reaction is 60-80 DEG C, reaction
Time is 2-4h；
In step (3), the temperature of reaction is 60-80 DEG C, and the time of reaction is 3-6h.
7. preparation method as claimed in claim 6, characterized in that in step (1), the temperature of reaction is 65-75 DEG C.
8. preparation method as claimed in claim 6, characterized in that in step (3), the temperature of reaction is 65-75 DEG C.
9. preparation method as claimed in claim 2, characterized in that specifically includes the following steps:
(1) octadecylamine is added in reaction vessel, isopropanol, heating stirring dissolution is added, then propylene oxide is added portionwise, adds
After entering, it is stirred to react 2-4h at 60-80 DEG C, obtains reaction intermediate I；
(2) sodium dihydrogen phosphate is added in another reaction vessel, adds water, heating stirring dissolution, then epoxy chloropropionate is added portionwise
Alkane after addition, is stirred to react 5-8h at 75-95 DEG C, obtains reaction intermediate II；
(3) reaction intermediate II is added portionwise in reaction intermediate I, 60-80 DEG C of reaction 3-6h to get arrive quaternary
Hydroxypropyl phosphate ester sodium asphalt emulsifier；
Or, specifically comprising the following steps:
(1) octadecylamine is added in reaction vessel, isopropanol, heating stirring dissolution is added, then propylene oxide is added portionwise, adds
After entering, it is stirred to react 2-4h at 60-80 DEG C, obtains reaction intermediate I；
(2) tertiary sodium phosphate is added in another reaction vessel, adds water, heating stirring dissolution, then epoxychloropropane is added portionwise,
After addition, it is stirred to react 5h at 42 DEG C, obtains reaction intermediate III；
(3) reaction intermediate III is added in reaction intermediate I, then hydrochloric acid is added portionwise, in 60-80 DEG C of reaction 3-6h, i.e.,
Obtain quaternary Hydroxypropyl phosphate ester sodium asphalt emulsifier.
10. quaternary Hydroxypropyl phosphate ester sodium asphalt emulsifier described in claim 1 or claim 2~9 are any described
Preparation method obtain quaternary Hydroxypropyl phosphate ester sodium asphalt emulsifier preparing the application in emulsified asphalt.
11. application as claimed in claim 10, it is characterized in that: the asphalt emulsifier splits the cation emulsified drip of type in preparation fastly
Application in blueness.
12. a kind of preparation method of cationic emulsified bitumen, characterized in that the following steps are included: the dosage of asphalt emulsifier is
The 1.0-3.0% of the emulsified asphalt gross mass of preparation, asphalt emulsifier described in claim 1 or claim 2~9 is any
The asphalt emulsifier that the preparation method obtains adds water to be configured to aqueous solution, adjusts pH value to 2-3 with technical hydrochloric acid, is heated to
60-70 DEG C, soap lye is made；By after heating pitch and emulsifier soap lye by colloid mill emulsification prepare cation emulsified drip
It is green.
13. the cationic emulsified bitumen being prepared using preparation method described in claim 12.
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| CN105418942A (en) * | 2015-12-21 | 2016-03-23 | 山东大学 | Dicationic amide type asphalt emulsifier and preparation method therefor |
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| CN105418942A (en) * | 2015-12-21 | 2016-03-23 | 山东大学 | Dicationic amide type asphalt emulsifier and preparation method therefor |
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