CN109694481A - A kind of carboxylic acid double quaternary ammonium salt type Hydroxypropyl phosphate ester sodium asphalt emulsifier and preparation method thereof - Google Patents
A kind of carboxylic acid double quaternary ammonium salt type Hydroxypropyl phosphate ester sodium asphalt emulsifier and preparation method thereof Download PDFInfo
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- CN109694481A CN109694481A CN201710984442.8A CN201710984442A CN109694481A CN 109694481 A CN109694481 A CN 109694481A CN 201710984442 A CN201710984442 A CN 201710984442A CN 109694481 A CN109694481 A CN 109694481A
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- 239000010426 asphalt Substances 0.000 title claims abstract description 148
- 239000003995 emulsifying agent Substances 0.000 title claims abstract description 107
- 238000002360 preparation method Methods 0.000 title claims abstract description 57
- 239000011734 sodium Substances 0.000 title claims abstract description 57
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 54
- 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 53
- 150000002148 esters Chemical class 0.000 title claims abstract description 50
- 150000003242 quaternary ammonium salts Chemical class 0.000 title claims abstract description 40
- HYCSHFLKPSMPGO-UHFFFAOYSA-N 3-hydroxypropyl dihydrogen phosphate Chemical compound OCCCOP(O)(O)=O HYCSHFLKPSMPGO-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title claims description 39
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 30
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims abstract description 24
- 235000019441 ethanol Nutrition 0.000 claims abstract description 24
- 125000002091 cationic group Chemical group 0.000 claims abstract description 23
- 239000003760 tallow Substances 0.000 claims abstract description 22
- 150000001298 alcohols Chemical class 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 21
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims abstract description 14
- 235000019799 monosodium phosphate Nutrition 0.000 claims abstract description 14
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims abstract description 14
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims abstract description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000005909 ethyl alcohol group Chemical group 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 63
- 239000007806 chemical reaction intermediate Substances 0.000 claims description 62
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Substances [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 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 22
- 229910019142 PO4 Inorganic materials 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000000344 soap Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 238000004945 emulsification Methods 0.000 claims description 12
- 239000010452 phosphate Substances 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 10
- 238000004090 dissolution Methods 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000000543 intermediate Substances 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000003292 glue Substances 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- UAJFTICTIXLVSD-UHFFFAOYSA-N P(=O)(O)(O)O.OCCC[Na] Chemical compound P(=O)(O)(O)O.OCCC[Na] UAJFTICTIXLVSD-UHFFFAOYSA-N 0.000 claims 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- VIRPUNZTLGQDDV-UHFFFAOYSA-N chloro propanoate Chemical compound CCC(=O)OCl VIRPUNZTLGQDDV-UHFFFAOYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 7
- 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
- 150000001735 carboxylic acids Chemical class 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- 238000001514 detection method Methods 0.000 description 11
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 9
- 125000000129 anionic group Chemical group 0.000 description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 5
- -1 betaine compound Chemical class 0.000 description 5
- 150000001768 cations Chemical group 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 229960003237 betaine Drugs 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- VLBVCFYCZMWOQF-UHFFFAOYSA-M CCCOP([O-])(OO)=O.[Na+] Chemical compound CCCOP([O-])(OO)=O.[Na+] VLBVCFYCZMWOQF-UHFFFAOYSA-M 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-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
- 238000004458 analytical method Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 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
- 239000004094 surface-active agent 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
- 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
- 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
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-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
- 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 1
- 239000003929 acidic solution Substances 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
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 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
- 239000006185 dispersion Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 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
- 239000007788 liquid Substances 0.000 description 1
- 238000005461 lubrication Methods 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
- 150000003016 phosphoric acids Chemical class 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
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010200 validation analysis Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- 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
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
- C08L95/005—Aqueous compositions, e.g. emulsions
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Civil Engineering (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Dispersion Chemistry (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The invention discloses a kind of carboxylic acid double quaternary ammonium salt type Hydroxypropyl phosphate ester sodium asphalt emulsifiers and preparation method thereof, the asphalt emulsifier is prepared by the raw material of following mol ratio: N- hydrogenated-tallow group -1,3- trimethylene diamines, alcohols solvent, acrylic acid, epoxychloropropane, sodium dihydrogen phosphate molar ratio be 1mol:(5.00-11.00) mol:(3.00-3.10) mol:(2.00-2.30) mol:(3.00-3.45) mol.Or, N- hydrogenated-tallow group -1,3- trimethylene diamines, alcohols solvent, acrylic acid, epoxychloropropane, tertiary sodium phosphate, hydrochloric acid molar ratio be 1mol:(5.00-11.00) mol:(3.00-3.10) mol:(2.00-2.30) mol:(2.60-2.99): (2.66-3.06) mol.The alcohols solvent is ethyl alcohol, methanol or isopropanol.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 carboxylic acid double quaternary ammonium salt type Hydroxypropyl phosphate ester sodium asphalt emulsifiers and preparation method thereof, belong to
Technical field of fine.
Background technique
Asphalt emulsifier is the surfactant for asphalt emulsification, and the surface tension of water can be made when small amount is added
It significantly reduces, it can substantially change the interfacial property and state of system, to generate wetting, emulsification, blistering, dispersion, resist
A series of effects such as electrostatic, lubrication, to reach the requirement of practical application.
In road engineering, emulsified asphalt be suitable for bituminous pavement top dressing, Cold bituminous mixture and permeable layers,
Adhesion coating and sealing have effects that save the energy, extend construction seasons, raising, improve execution conditions, reduce environmental pollution etc. excellent
Point.The classification method of asphalt emulsifier is more, mainly includes anionic, cationic, nonionic according to ionic type classification
Type and amphoteric.Amphoteric is mainly betaine compound, imidazolines and amino acids.
But the exploitation in relation to both sexes asphalt emulsifier is later, and kind and quantity are all few.United States Patent (USP) USP3342840 is situated between
Continuing and having synthesized a kind of hydrophilic group is amino and the simultaneous amphoteric emulsifier of hydroxyl, but the preparation cost of the emulsifier compared with
It is high.Chinese patent CN101712625A is related to a kind of method for synthesizing amphoteric slow-breaking quick-setting asphalt emulsifier, using oleic acid and polyamines
Reaction generates polyamide-polyamino, and monoxone is then added, and asphalt emulsifier is made.The disadvantages of the method are as follows needing high temperature anti-when preparation
It answers.
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 carboxylic acid double quaternary ammonium salt type Hydroxypropyl phosphate ester sodium asphalt emulsifier and preparation method thereof of pyroreaction is not needed.
The first aspect of the invention provides a kind of carboxylic acid double quaternary ammonium salt type 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:
The carboxylic acid double quaternary ammonium salt type Hydroxypropyl phosphate ester sodium asphalt emulsifier is in the application for preparing emulsified asphalt, especially,
The application in type cationic emulsified bitumen is split fastly in preparation.
The second aspect of the invention provides a kind of system of carboxylic acid double quaternary ammonium salt type Hydroxypropyl phosphate ester sodium asphalt emulsifier
Preparation Method, comprising the following steps:
(1) by N- hydrogenated-tallow group -1,3- trimethylene diamines, alcohols solvent and acrylic acid hybrid reaction, it is intermediate to obtain reaction
Body I, the structural formula of the reaction intermediate I are
(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 carboxylic acid double quaternary ammonium salt type hydroxyl
Propyl phosphate sodium asphalt emulsifier；
Or, the following steps are included:
(1) by N- hydrogenated-tallow group -1,3- trimethylene diamines, alcohols solvent and acrylic acid hybrid reaction, it is intermediate to obtain reaction
Body I, the structural formula of the reaction intermediate I are
(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
Carboxylic acid double quaternary ammonium salt type 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 acrylic acid is added in raw material of the invention, so that the asphalt emulsification agent molecule that the present invention is prepared
Hydrophily is larger；The addition of epoxychloropropane and sodium dihydrogen phosphate (or tertiary sodium phosphate) makes the asphalt emulsifier being prepared point
Son has carboxylic acid double quaternary ammonium salt type 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, quaternary ammonium salt and carboxyl,
So that interfacial film, hydration layer and interface charge layer all enhance accordingly, emulsion intercalation method is improved.
(2) present invention using specific raw material propylene acid, N- hydrogenated-tallow group -1,3- trimethylene diamines, epoxychloropropane and
Sodium dihydrogen phosphate (or tertiary sodium phosphate) generates the asphalt emulsifier with certain HLB value, using carboxylic acid prepared by the present invention double seasons
Ammonium salt type Hydroxypropyl phosphate ester sodium asphalt emulsifier has good emulsifiability, the properties for the emulsified asphalt being prepared
Index is excellent, the pitch of emulsifiable a variety of different models, and the emulsified asphalt of preparation is fine and smooth uniformly, have it is good gather materials wrap up in attached property
And storage stability.Emulsified asphalt obtained presses the cationic emulsified bitumen professional standard (JTJ052- that Chinese transportation portion works out
2000) it is detected, properties are able to satisfy standard requirements.Suitable for the spread of highway priming oil or sticking layer oil, Yi Jiyong
In crushed stone sealing, screening seal coat, mist sealing and reparation slight check crack in road surface etc., there is the characteristic for splitting asphalt emulsifier fastly.
(3) the raw material N- hydrogenated-tallow group-of carboxylic acid double quaternary ammonium salt type Hydroxypropyl phosphate ester sodium asphalt emulsifier of the invention
1,3- trimethylene diamines is cheap, from a wealth of sources relative to raw material used in current cationic asphalt emulsifier, 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 carboxylic acid double quaternary ammonium salt type 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 carboxylic acid double quaternary ammonium salt type 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:
The structure for analyzing the carboxylic acid double quaternary ammonium salt type Hydroxypropyl phosphate ester sodium asphalt emulsifier, by multiple hydroxyls, phosphoric acid
Salt, quaternary ammonium salt and carboxylated hydrophilic group are effectively combined in the form of certain group, in addition suitable carbon-chain structure and its
His lipophilic group, is collectively formed this new structural asphalt emulsifier.
For the above asphalt emulsifier, the present invention also provides its preparation methods, comprising the following steps:
(1) by N- hydrogenated-tallow group -1,3- trimethylene diamines, alcohols solvent and acrylic acid hybrid reaction, it is intermediate to obtain reaction
Body I, the structural formula of the reaction intermediate I are
(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 carboxylic acid double quaternary ammonium salt type hydroxyl
Propyl phosphate sodium asphalt emulsifier；
Or, the following steps are included:
(1) by N- hydrogenated-tallow group -1,3- trimethylene diamines, alcohols solvent and acrylic acid hybrid reaction, it is intermediate to obtain reaction
Body I, the structural formula of the reaction intermediate I are
(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
Carboxylic acid double quaternary ammonium salt type 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, N- hydrogenated-tallow group -1,3- trimethylene diamines, alcohols solvent, propylene
Acid, epoxychloropropane, sodium dihydrogen phosphate molar ratio be 1mol:(5.00-11.00) mol:(3.00-3.10) mol:(2.00-
2.30) mol:(3.00-3.45) mol.
In some preferred technical solutions of the present invention, N- hydrogenated-tallow group -1,3- trimethylene diamines, alcohols solvent, propylene
Acid, epoxychloropropane, tertiary sodium phosphate, hydrochloric acid molar ratio be 1mol:(5.00-11.00) mol:(3.00-3.10) mol:
(2.00-2.30) mol:(2.60-2.99): (2.66-3.06) mol.
By lot of experiment validation and analysis, the carboxylic acid that the present invention is prepared in each raw material of above-mentioned molar ratio is double
The performance of quaternary Hydroxypropyl phosphate ester sodium asphalt emulsifier is more satisfactory, and the raw material of inappropriate proportion relation cannot form carboxylic
Sour double quaternary ammonium salt type Hydroxypropyl phosphate ester sodium asphalt emulsifier.
In some preferred technical solutions of the present invention, the alcohols solvent is ethyl alcohol, methanol or isopropanol, by a large amount of
Experimental verification and analysis, and the need of carboxylic acid double quaternary ammonium salt type Hydroxypropyl phosphate ester sodium asphalt emulsifier obtained according to the present invention
It wants, selects the effect of asphalt emulsifier made from above-mentioned alcohols solvent preferable.
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 carboxylic acid double quaternary ammonium salt type Hydroxypropyl phosphate ester sodium asphalt emulsification
The preparation method of agent, specifically comprises the following steps:
(1) N- hydrogenated-tallow group -1,3- trimethylene diamines is added in reaction vessel, alcohols solvent, heating stirring is added
Dissolution, then acrylic acid is added portionwise, after addition, 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 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 carboxylic acid
Double quaternary ammonium salt type Hydroxypropyl phosphate ester sodium asphalt emulsifier；
Or, specifically comprising the following steps:
(1) N- hydrogenated-tallow group -1,3- trimethylene diamines is added in reaction vessel, alcohols solvent, heating stirring is added
Dissolution, then acrylic acid is added portionwise, after addition, 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 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 carboxylic acid double quaternary ammonium salt type Hydroxypropyl phosphate ester sodium asphalt emulsifier.
Above-mentioned carboxylic acid double quaternary ammonium salt type Hydroxypropyl phosphate ester sodium asphalt emulsifier is preparing the application in emulsified asphalt, especially
It is to split the application in type cationic emulsified bitumen fastly in preparation.
Reaction raw materials of the present invention using acrylic acid as asphalt emulsifier, by adding in the molecular structure of asphalt emulsifier
Enter acrylic acid and introduce carboxyl, increases the hydrophily of asphalt emulsifier and the compatibility of emulsifier and pitch.In addition, comprehensive
It closes and considers carbon chain lengths for the shadow of HLB value (the hydrophilic/lipophilic balance value) and CMC (critical micelle concentration) of asphalt emulsifier
It rings, selection is with N- hydrogenated-tallow group -1,3- trimethylene diamines, epoxychloropropane and sodium dihydrogen phosphate (or tertiary sodium phosphate) as reaction
Raw material, make preparation asphalt emulsifier HLB value within optimum range, improve the emulsifiability to pitch.
For the carboxylic acid double quaternary ammonium salt type Hydroxypropyl phosphate ester sodium asphalt emulsifier in the present invention, the present invention also provides one kind
The preparation method of cationic emulsified bitumen includes the following steps: that the dosage of asphalt emulsifier is the emulsified asphalt gross mass of preparation
1.0-3.0%, add water to be configured to aqueous solution above-mentioned asphalt emulsifier, with technical hydrochloric acid adjust pH value to 2-3, be 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.
The cationic emulsified bitumen that above-mentioned preparation method is prepared.
For the carboxylic acid double quaternary ammonium salt type Hydroxypropyl phosphate ester sodium asphalt emulsifier in the present invention, the present invention also provides one kind
The preparation method of anionic emulsified bitumen includes the following steps: that the dosage of asphalt emulsifier is the emulsified asphalt gross mass of preparation
1.0-3.0%, add water to be configured to aqueous solution above-mentioned asphalt emulsifier, with sodium hydroxide adjust pH value to 10-11, be heated to
60-70 DEG C, soap lye is made；By after heating pitch and emulsifier soap lye by colloid mill emulsification prepare anionic emulsifying drip
It is green.
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 carboxylic acid double quaternary ammonium salt type Hydroxypropyl phosphate ester sodium asphalt emulsifier:
1) 326.0g N- hydrogenated-tallow group -1,3- trimethylene diamines, 330g isopropanol, heating stirring are added in the reactor
Dissolution.Then it is gradually added into 219.8g acrylic acid, 70 DEG C are stirred to react 3h.
2) 491.4g sodium dihydrogen phosphate (NaH is added in another reactor2PO4·2H2O) and 966g water, stirring and dissolving,
It is heated to 85 DEG C.194.1g epoxychloropropane is added dropwise again, 85 DEG C are stirred to react 7.5h, obtain 3- chlorine-2-hydroxyl propyl phosphate
Sodium water 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.Carboxylic acid double quaternary ammonium salt type Hydroxypropyl phosphate ester sodium asphalt emulsifier is obtained, emulsified asphalt examination is given over to
It tests.
Synthetic product carries out FTIR detection after recrystallizing separating-purifying, as a result as follows: 3434cm-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, 1727cm-1For C=O symmetrical stretching vibration absorption peak in saturation carboxyl, 1584cm-1For C-O asymmetric stretch in carboxyl
Vibration absorption peak, 1470cm-1It is vibrated for the asymmetric curvature of methylene, 1400cm-1It is vibrated for the asymmetric curvature of methyl,
1230cm-1For P=O stretching vibration absworption peak, 1048cm-1For the stretching vibration absworption peak of P-O-R, 718cm-1For methylene basal plane
Interior rocking 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
0.02%, 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 4 seconds the mixing time.
The asphalt emulsion for showing emulsifier preparation is to split type cationic emulsified bitumen fastly, and properties are able to satisfy standard requirements.
Embodiment 2
(1) preparation of carboxylic acid double quaternary ammonium salt type Hydroxypropyl phosphate ester sodium asphalt emulsifier:
1) 326.0g N- hydrogenated-tallow group -1,3- trimethylene diamines, 330g isopropanol, heating stirring are added in the reactor
Dissolution.Then it is gradually added into 219.8g acrylic acid, 70 DEG C are stirred to react 3h.
2) 1037.7g tertiary sodium phosphate (Na is added in another reactor3PO4·12H2O) and 1344g water, stirring and dissolving,
It is heated to 42 DEG C.194.1g 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 340.2g hydrochloric acid (30%), 75 DEG C are stirred to react 3h.Carboxylic acid double quaternary ammonium salt type Hydroxypropyl phosphate ester sodium asphalt emulsifier is obtained,
Give over to emulsified asphalt test.
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, 2918cm-1For the asymmetric stretching vibration absworption peak of methylene, 2846cm-1For the symmetrical stretching vibration of methylene
Receive peak, 1737cm-1For the symmetrical stretching vibration absorption peak of C=O in saturation carboxyl, 1628cm-1It is stretched for C-O asymmetry in carboxyl
Contracting vibration absorption peak, 1476cm-1For the asymmetric curvature vibration absorption peak of methylene, 1373cm-1For the asymmetric curvature of methyl
Vibration, 1220cm-1For the stretching vibration absworption peak of P=O, 1054cm-1For the stretching vibration absworption peak of P-O-R, 723cm-1For Asia
Methyl rocking 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 60%, remains on sieve
Surplus is 0.02%, 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 5 seconds.The asphalt emulsion for showing emulsifier preparation is to split type cationic emulsified bitumen fastly, and properties are able to satisfy standard and want
It asks.
Embodiment 3
(1) preparation of carboxylic acid double quaternary ammonium salt type Hydroxypropyl phosphate ester sodium asphalt emulsifier:
1) 326.0g N- hydrogenated-tallow group -1,3- trimethylene diamines, 330g dehydrated alcohol are added in the reactor, heating is stirred
Mix dissolution.Then it is gradually added into 219.8g acrylic acid, 65 DEG C are stirred to react 4h.
2) 491.4g sodium dihydrogen phosphate (NaH is added in another reactor2PO4·2H2O) and 966g water, stirring and dissolving,
It is heated to 85 DEG C.194.1g epoxychloropropane is added dropwise again, 85 DEG C are stirred to react 7.5h, obtain 3- chlorine-2-hydroxyl propyl phosphate
Sodium water 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, 60 DEG C are stirred to react 6h.Carboxylic acid double quaternary ammonium salt type Hydroxypropyl phosphate ester sodium asphalt emulsifier is obtained, emulsified asphalt examination is given over to
It tests.
(2) preparation of emulsified asphalt:
A-100# 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 properties are able to satisfy standard and want
It asks.
Comparative example 1
(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 2
(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 3
(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: 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 1-2
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 (10)
1. a kind of carboxylic acid double quaternary ammonium salt type Hydroxypropyl phosphate ester sodium asphalt emulsifier, characterized in that the carboxylic acid double quaternary ammonium salt type
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 carboxylic acid double quaternary ammonium salt type Hydroxypropyl phosphate ester sodium asphalt emulsifier described in claim 1, feature
It is, comprising the following steps:
(1) by N- hydrogenated-tallow group -1,3- trimethylene diamines, alcohols solvent and acrylic acid hybrid reaction, reaction intermediate I is obtained,
The structural formula of the reaction intermediate I is
(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 carboxylic acid double quaternary ammonium salt type hydroxypropyl
Sodium phosphate asphalt emulsifier；
Or, the following steps are included:
(1) by N- hydrogenated-tallow group -1,3- trimethylene diamines, alcohols solvent and acrylic acid hybrid reaction, reaction intermediate I is obtained,
The structural formula of the reaction intermediate I is
(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 carboxylic acid
Double quaternary ammonium salt type Hydroxypropyl phosphate ester sodium asphalt emulsifier.
3. preparation method as claimed in claim 2, characterized in that reaction intermediate II (the 3- chlorine-2-hydroxyl propyl phosphoric acid
Ester sodium) preparation method, the temperature of reaction is 75-95 DEG C, and preferably 80-90 DEG C, the time of reaction is 5-8h；
The preparation method of the reaction intermediate III (phosphate epoxypropyl ester sodium), the temperature of reaction are 42 DEG C, the time of reaction
For 5h.
4. preparation method as claimed in claim 2, characterized in that N- hydrogenated-tallow group -1,3- trimethylene diamines, alcohols solvent,
Acrylic acid, epoxychloropropane, sodium dihydrogen phosphate molar ratio be 1mol:(5.00-11.00) mol:(3.00-3.10) mol:
(2.00-2.30) mol:(3.00-3.45) mol；
N- hydrogenated-tallow group -1,3- trimethylene diamines, alcohols solvent, acrylic acid, epoxychloropropane, tertiary sodium phosphate, hydrochloric acid mole
Than being 1mol:(5.00-11.00) mol:(3.00-3.10) mol:(2.00-2.30) mol:(2.60-2.99): (2.66-
3.06)mol；Preferably, alcohols solvent is ethyl alcohol, methanol or isopropanol.
5. preparation method as claimed in claim 2, characterized in that 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 step (3), the temperature of reaction is 60-80 DEG C, and preferably 65-75 DEG C, the time of reaction is 3-6h.
6. preparation method as claimed in claim 2, characterized in that specifically includes the following steps:
(1) N- hydrogenated-tallow group -1,3- trimethylene diamines being added in reaction vessel, alcohols solvent is added, heating stirring dissolves,
Acrylic acid is added portionwise again, 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 chloropropionate is added portionwise
Alkane after addition, is stirred to react 5-8h at 75-95 DEG C, obtains reaction intermediate II (3- chlorine-2-hydroxyl propyl phosphate
Sodium)；
(3) reaction intermediate II is added portionwise in reaction intermediate I, in 60-80 DEG C of reaction 3-6h to get to carboxylic acid double seasons
Ammonium salt type Hydroxypropyl phosphate ester sodium asphalt emulsifier；
Or, specifically comprising the following steps:
(1) N- hydrogenated-tallow group -1,3- trimethylene diamines being added in reaction vessel, alcohols solvent is added, heating stirring dissolves,
Acrylic acid is added portionwise again, 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 epoxychloropropane is added portionwise,
After addition, it 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, i.e.,
Obtain carboxylic acid double quaternary ammonium salt type Hydroxypropyl phosphate ester sodium asphalt emulsifier.
7. carboxylic acid double quaternary ammonium salt type Hydroxypropyl phosphate ester sodium asphalt emulsifier described in claim 1 is in preparing emulsified asphalt
Using.
8. the use as claimed in claim 7, it is characterized in that: the asphalt emulsifier splits type cationic emulsified bitumen in preparation fastly
In application.
9. a kind of preparation method of cationic emulsified bitumen, characterized in that the following steps are included: the dosage of asphalt emulsifier is system
Asphalt emulsifier described in claim 1 is added water to be configured to aqueous solution by the 1.0-3.0% of standby emulsified asphalt gross mass, is used
Nacl acid for adjusting pH value is heated to 60-70 DEG C, soap lye is made to 2-3；By after heating pitch and emulsifier soap lye pass through glue
Cationic emulsified bitumen is prepared in body mill emulsification.
10. the cationic emulsified bitumen being prepared using preparation method as claimed in claim 9.
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| CN201710984442.8A CN109694481B (en) | 2017-10-20 | 2017-10-20 | Carboxylic acid bis-quaternary ammonium salt type sodium hydroxypropyl phosphate asphalt emulsifier and preparation method thereof |
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| CN201710984442.8A CN109694481B (en) | 2017-10-20 | 2017-10-20 | Carboxylic acid bis-quaternary ammonium salt type sodium hydroxypropyl phosphate asphalt emulsifier and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113083152A (en) * | 2021-04-20 | 2021-07-09 | 山东大学 | Carboxylic acid sulfonic acid type surfactant, and preparation method and application thereof |
| CN113429560A (en) * | 2021-07-12 | 2021-09-24 | 江苏海洋大学 | Multifunctional polyquaternary ammonium salt and preparation method thereof |
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| WO2011000897A1 (en) * | 2009-07-02 | 2011-01-06 | Basf Se | Co-agglomerated latex polymer dispersions and methods of preparing and using same |
| CN103788662A (en) * | 2012-10-29 | 2014-05-14 | 中国石油化工股份有限公司 | Emulsified asphalt, a preparation method thereof, applications thereof, a water-proof coating material and a water-proof coating |
| CN106946747A (en) * | 2017-04-13 | 2017-07-14 | 山东大学 | A kind of carboxylic acid double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier and preparation method thereof |
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| WO2011000897A1 (en) * | 2009-07-02 | 2011-01-06 | Basf Se | Co-agglomerated latex polymer dispersions and methods of preparing and using same |
| CN103788662A (en) * | 2012-10-29 | 2014-05-14 | 中国石油化工股份有限公司 | Emulsified asphalt, a preparation method thereof, applications thereof, a water-proof coating material and a water-proof coating |
| CN106946747A (en) * | 2017-04-13 | 2017-07-14 | 山东大学 | A kind of carboxylic acid double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113083152A (en) * | 2021-04-20 | 2021-07-09 | 山东大学 | Carboxylic acid sulfonic acid type surfactant, and preparation method and application thereof |
| CN113429560A (en) * | 2021-07-12 | 2021-09-24 | 江苏海洋大学 | Multifunctional polyquaternary ammonium salt and preparation method thereof |
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