CN111848980A - A kind of ester group-containing polyamine quaternary ammonium salt type asphalt emulsifier, emulsified asphalt and its preparation method and application - Google Patents
A kind of ester group-containing polyamine quaternary ammonium salt type asphalt emulsifier, emulsified asphalt and its preparation method and application Download PDFInfo
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- 239000010426 asphalt Substances 0.000 title claims abstract description 169
- 239000003995 emulsifying agent Substances 0.000 title claims abstract description 106
- 229920000768 polyamine Polymers 0.000 title claims abstract description 61
- 150000003242 quaternary ammonium salts Chemical class 0.000 title claims abstract description 40
- 125000004185 ester group Chemical group 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 125000002091 cationic group Chemical group 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims description 57
- 239000007806 chemical reaction intermediate Substances 0.000 claims description 46
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 32
- 150000001875 compounds Chemical class 0.000 claims description 27
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 24
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 20
- 150000002148 esters Chemical class 0.000 claims description 18
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 17
- 239000000194 fatty acid Substances 0.000 claims description 17
- 229930195729 fatty acid Natural products 0.000 claims description 17
- 150000004665 fatty acids Chemical class 0.000 claims description 17
- 239000003784 tall oil Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 8
- 239000008149 soap solution Substances 0.000 claims description 8
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 6
- 239000000084 colloidal system Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 claims description 5
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 5
- 230000001476 alcoholic effect Effects 0.000 claims description 4
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims 3
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical compound CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 claims 1
- 150000001768 cations Chemical class 0.000 claims 1
- 230000001804 emulsifying effect Effects 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000000543 intermediate Substances 0.000 claims 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims 1
- 229960001124 trientine Drugs 0.000 claims 1
- 238000005336 cracking Methods 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 description 35
- 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 description 14
- 238000005452 bending Methods 0.000 description 13
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 13
- 238000004945 emulsification Methods 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 125000001453 quaternary ammonium group Chemical class 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000004891 communication Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- 238000012795 verification Methods 0.000 description 3
- 229910014033 C-OH Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910014570 C—OH Inorganic materials 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000006414 CCl Chemical group ClC* 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002193 fatty amides Chemical class 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000010507 melon oil Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/04—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reaction of ammonia or amines with olefin oxides or halohydrins
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/12—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms
- C07D295/125—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
- C07D295/13—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/27—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/27—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms
- C07D301/30—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms by reaction with carboxyl radicals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/16—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by esterified hydroxyl radicals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/36—Compounds containing oxirane rings with hydrocarbon radicals, substituted by nitrogen atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2395/00—Bituminous materials, e.g. asphalt, tar or pitch
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- Dispersion Chemistry (AREA)
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- Polymers & Plastics (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明提供一种含酯基多胺季铵盐型沥青乳化剂、乳化沥青及其制备方法与应用，该沥青乳化剂的分子结构通式为：式X：
Description
技术领域technical field
本发明涉及精细化工技术领域，具体涉及一种含酯基多胺季铵盐型沥青乳化剂、乳化沥青及其制备方法与应用。The invention relates to the technical field of fine chemicals, in particular to an ester group-containing polyamine quaternary ammonium salt type asphalt emulsifier, an emulsified asphalt and a preparation method and application thereof.
背景技术Background technique
公开该背景技术部分的信息仅仅旨在增加对本发明的总体背景的理解，而不必然被视为承认或以任何形式暗示该信息构成已经成为本领域一般技术人员所公知的现有技术。The information disclosed in this Background section is only for enhancement of understanding of the general background of the invention and should not necessarily be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person of ordinary skill in the art.
目前国内外阳离子型沥青乳化剂主要品种有：有机胺类、季铵盐类、咪唑啉类、酰胺类等，随着阳离子乳化沥青的应用，沥青乳化剂的品种也逐渐丰富。At present, the main varieties of cationic asphalt emulsifiers at home and abroad are: organic amines, quaternary ammonium salts, imidazolines, amides, etc. With the application of cationic emulsified asphalt, the varieties of asphalt emulsifiers are gradually enriched.
安磊等人通过不同的多乙烯多胺和不同的酸混合反应制备了混合酰胺型沥青乳化剂，并对沥青乳化性能进行测试，结果表明制备的沥青乳化剂属于慢裂快凝型乳化剂，并且混合类沥青乳化剂比单一类沥青乳化剂乳化效果好[安磊,崔巍,王宝彗,王冬美.混合多乙烯多胺型沥青乳化剂的合成及其性能测试.中国高新技术企业,2011,(31):58-59]。郭彦强等人从分子结构设计出发制备了脂肪酰胺沥青乳化剂。通过对性能测试实验，观察沥青的乳化情况及新制备乳化沥青的拌和性能，来研究所合成沥青乳化剂的性能。结果表明所研制的乳化剂可以很好的将SK-90沥青进行乳化，制备出的乳化沥青具有分散性好的特点[郭彦强,韩瑞民,弥海晨,弓锐.脂肪酰胺阳离子沥青乳化剂的合成及性能.公路,2014,59(11):193-196]。王冬美等人采用三乙烯四胺，硬脂酸和瓜子油脂肪酸合成了一种混合酰胺型阳离子沥青乳化剂，通过正交实验优化了合成沥青乳化剂的工艺条件。通过性能测试，结果表明所制备的沥青乳化剂为慢裂快凝型沥青乳化剂，具有乳化性能好、用量少、与集料粘附力强、适应性强、附着速度快、储存稳定性好等特点[王冬美,安磊,张建中,崔巍,许云峰,佟天宇.一种酰胺类阳离子沥青乳化剂的合成及应用.石油化工高等学校学报,2015,28(1):16-19]。An Lei et al. prepared mixed amide-type asphalt emulsifiers through the mixed reaction of different polyethylene polyamines and different acids, and tested the emulsification performance of asphalt. And mixed asphalt emulsifiers have better emulsification effect than single asphalt emulsifiers [An Lei, Cui Wei, Wang Baohui, Wang Dongmei. Synthesis and Performance Test of Mixed Polyethylene Polyamine Asphalt Emulsifiers. China High-tech Enterprise, 2011 , (31):58-59]. Guo Yanqiang et al prepared fatty amide asphalt emulsifier from molecular structure design. The performance of the synthetic asphalt emulsifier was studied by observing the emulsification of the asphalt and the mixing performance of the newly prepared emulsified asphalt through performance testing experiments. The results show that the developed emulsifier can emulsify SK-90 asphalt well, and the prepared emulsified asphalt has the characteristics of good dispersibility [Guo Yanqiang, Han Ruimin, Mi Haichen, Gong Rui. Synthesis of Fatty Amide Cationic Asphalt Emulsifier and Performance. Highways, 2014, 59(11):193-196]. Wang Dongmei et al. synthesized a mixed amide type cationic asphalt emulsifier using triethylenetetramine, stearic acid and melon seed oil fatty acid, and optimized the process conditions of the synthetic asphalt emulsifier through orthogonal experiments. Through the performance test, the results show that the prepared asphalt emulsifier is a slow-cracking and fast-setting asphalt emulsifier, which has good emulsification performance, low dosage, strong adhesion to aggregates, strong adaptability, fast adhesion speed, and storage stability. Hao et al. [Wang Dongmei, An Lei, Zhang Jianzhong, Cui Wei, Xu Yunfeng, Tong Tianyu. Synthesis and Application of an Amide Cationic Asphalt Emulsifier. Journal of Petrochemical Universities, 2015, 28(1): 16-19].
但是，发明人发现，这些方法的缺点是合成工艺中需要高温反应，反应步骤较繁琐，原料来源受到限制，对生产实验设备要求较高。However, the inventors found that the disadvantages of these methods are that high temperature reaction is required in the synthesis process, the reaction steps are cumbersome, the source of raw materials is limited, and the requirements for production experimental equipment are relatively high.
发明内容SUMMARY OF THE INVENTION
因此，针对上述阳离子型沥青乳化剂及其制备方法存在的不足，即合成工艺中需要高温反应，反应步骤较繁琐，原料来源受到限制，对生产实验设备要求较高的问题，本发明的目的在于提供一种生产成本低、工艺简单、不需要高温反应的含酯基多胺季铵盐型沥青乳化剂及其制备方法。Therefore, in view of the shortcomings of the above-mentioned cationic asphalt emulsifier and its preparation method, that is, high temperature reaction is required in the synthesis process, the reaction steps are relatively trivial, the source of raw materials is limited, and the requirements for production experimental equipment are relatively high. The purpose of the present invention is to Provided are an ester group-containing polyamine quaternary ammonium salt type asphalt emulsifier with low production cost, simple process and no high temperature reaction and a preparation method thereof.
为实现上述目的，本发明采用如下技术方案：To achieve the above object, the present invention adopts the following technical solutions:
在本发明的第一方面，提供一种含酯基多胺季铵盐型沥青乳化剂，其具有式X所示的分子结构通式，式X为：
其中，R为-NH(CH2CH2NH)m-H、
根据本发明所述的含酯基多胺季铵盐型沥青乳化剂，其可以选自以下结构：According to the ester group-containing polyamine quaternary ammonium salt type asphalt emulsifier of the present invention, it can be selected from the following structures:
在本发明的第二方面，提供一种第一方面所述含酯基多胺季铵盐型沥青乳化剂的制备方法，包括以下步骤：In the second aspect of the present invention, there is provided a preparation method of the ester group-containing polyamine quaternary ammonium salt type asphalt emulsifier described in the first aspect, comprising the following steps:
(1)将妥尔油脂肪酸、醇类溶剂和环氧氯丙烷混合反应，得到反应中间体I，所述反应中间体I的结构式为
(2)向反应中间体I中再逐渐加入多胺类化合物，混合反应，得到反应中间体II，所述反应中间体II的结构通式为(2) gradually adding polyamine compounds to the reaction intermediate I, and mixing the reaction to obtain the reaction intermediate II, the general structural formula of the reaction intermediate II is:
其中，R为-NH(CH2CH2NH)m-H、
(3)将三甲胺水溶液、盐酸和环氧氯丙烷混合反应，得到反应中间体III；(3) mixed reaction of trimethylamine aqueous solution, hydrochloric acid and epichlorohydrin to obtain reaction intermediate III;
(4)向反应中间体II中再逐渐加入反应中间体III，混合反应，即得到含酯基多胺季铵盐型沥青乳化剂。(4) The reaction intermediate III is gradually added to the reaction intermediate II, and the mixed reaction is performed to obtain an ester group-containing polyamine quaternary ammonium salt type asphalt emulsifier.
在本发明的第三方面，提供一种第一方面所述含酯基多胺季铵盐型沥青乳化剂在制备乳化沥青的应用，尤其是，本发明提供了上述第一方面中所述的季铵盐多胺两性型沥青乳化剂在制备慢裂型阳离子乳化沥青中的应用。In the third aspect of the present invention, an application of the ester-group-containing polyamine quaternary ammonium salt type asphalt emulsifier described in the first aspect is provided in the preparation of emulsified asphalt. In particular, the present invention provides the above-mentioned first aspect. The application of quaternary ammonium salt polyamine amphoteric asphalt emulsifier in the preparation of slow cracking cationic emulsified asphalt.
在本发明的第四方面，提供一种阳离子乳化沥青的制备方法，包括如下步骤：In the fourth aspect of the present invention, there is provided a preparation method of cationic emulsified asphalt, comprising the steps of:
将上述第一方面中所述的沥青乳化剂加水配制成水溶液，用工业盐酸调节pH值至2-3，加热至60-70℃，制得皂液；将加热后的沥青和乳化剂皂液通过胶体磨乳化制备出阳离子乳化沥青；其中，沥青乳化剂的用量为制备的乳化沥青总质量的1.0-3.0％。The asphalt emulsifier described in the first aspect above is added with water to prepare an aqueous solution, the pH value is adjusted to 2-3 with industrial hydrochloric acid, and heated to 60-70° C. to obtain a soap solution; the heated asphalt and the emulsifier soap solution are mixed. The cationic emulsified asphalt is prepared through colloid mill emulsification; wherein, the dosage of the asphalt emulsifier is 1.0-3.0% of the total mass of the prepared emulsified asphalt.
在本发明的第五方面，本发明保护上述第四方面中所述的制备方法制备得到的阳离子乳化沥青。In the fifth aspect of the present invention, the present invention protects the cationic emulsified asphalt prepared by the preparation method described in the fourth aspect above.
本发明的具体实施方式具有以下有益效果：The specific embodiment of the present invention has the following beneficial effects:
(1)本发明的具体实施方式中原料中通过加入多胺类化合物，使得本发明制备得到的沥青乳化剂分子的亲水性较大；环氧氯丙烷和妥尔油脂肪酸的加入，使制备得到的沥青乳化剂分子具有含酯基多胺季铵盐化学结构，增强了沥青乳化剂分子的电荷强度。(1) in the specific embodiment of the present invention, by adding polyamine compounds in the raw material, the hydrophilicity of the asphalt emulsifier molecule prepared by the present invention is larger; the addition of epichlorohydrin and tall oil fatty acid makes the preparation The obtained asphalt emulsifier molecule has the chemical structure of ester group-containing polyamine quaternary ammonium salt, which enhances the charge strength of the asphalt emulsifier molecule.
本发明的沥青乳化剂结构式中含有的亲水基较多，羟基、胺基、季铵盐和酯基，使得界面膜、水合层和界面电荷层都相应的增强，提高了乳液的稳定性。The structural formula of the asphalt emulsifier of the present invention contains more hydrophilic groups, such as hydroxyl groups, amine groups, quaternary ammonium salts and ester groups, so that the interfacial film, hydration layer and interfacial charge layer are correspondingly enhanced, and the stability of the emulsion is improved.
(2)本发明的具体实施方式中采用特定的原料三甲胺、多胺类化合物、环氧氯丙烷和妥尔油脂肪酸，生成具有一定HLB值的沥青乳化剂，采用本发明制备的含酯基多胺季铵盐型沥青乳化剂具有很好的乳化性能，制备得到的乳化沥青的性能指标优良，可乳化多种不同型号的沥青，制备的乳化沥青细腻均匀，具有良好的集料裹附性和储存稳定性。制得的乳化沥青按中国交通部制订的阳离子乳化沥青行业标准(JTJ052-2000)进行检测，性能满足要求。适用于公路稀浆封层和微表处等施工，具有慢裂沥青乳化剂的特性。(2) In the specific embodiment of the present invention, specific raw materials trimethylamine, polyamine compounds, epichlorohydrin and tall oil fatty acid are used to generate an asphalt emulsifier with a certain HLB value, and an ester-containing emulsifier prepared by the present invention is used. The polyamine quaternary ammonium salt type asphalt emulsifier has good emulsification performance, the prepared emulsified asphalt has excellent performance indicators, can emulsify a variety of different types of asphalt, the prepared emulsified asphalt is fine and uniform, and has good aggregate adhesion. and storage stability. The prepared emulsified asphalt is tested according to the industry standard of cationic emulsified asphalt (JTJ052-2000) formulated by the Ministry of Communications of China, and its performance meets the requirements. It is suitable for the construction of highway slurry seal and micro-surface, and has the characteristics of slow cracking asphalt emulsifier.
(3)本发明的具体实施方式中含酯基多胺季铵盐型沥青乳化剂的主原料妥尔油脂肪酸相对于目前的阳离子型沥青乳化剂所用的原料便宜、来源广泛，可生物降解，沥青乳化剂生产成本低。(3) Tall oil fatty acid, the main raw material of the ester group-containing polyamine quaternary ammonium salt-type asphalt emulsifier in the specific embodiment of the present invention, is cheaper, has a wide range of sources, and is biodegradable compared to the raw materials used in the current cationic asphalt emulsifier. The production cost of asphalt emulsifier is low.
(4)现有技术中酰胺基胺类乳化剂反应温度一般控制在140～180℃，而本发明的具体实施方式中含酯基多胺季铵盐型沥青乳化剂的制备方法工艺简单、不需要高温反应，降低能耗。(4) In the prior art, the reaction temperature of the amidoamine emulsifier is generally controlled at 140 to 180° C., while the preparation method of the ester-based polyamine quaternary ammonium salt-type asphalt emulsifier in the specific embodiment of the present invention is simple in process and not easy to use. High temperature reaction is required to reduce energy consumption.
具体实施方式Detailed ways
应该指出，以下详细说明都是示例性的，旨在对本发明提供进一步的说明。除非另有指明，本文使用的所有技术和科学术语具有与本发明所属技术领域的普通技术人员通常理解的相同含义。It should be noted that the following detailed description is exemplary and intended to provide further explanation of the invention. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
需要注意的是，这里所使用的术语仅是为了描述具体实施方式，而非意图限制根据本发明的示例性实施方式。如在这里所使用的，除非上下文另外明确指出，否则单数形式也意图包括复数形式，此外，还应当理解的是，当在本说明书中使用术语“包含”和/或“包括”时，其指明存在特征、步骤、操作、组件和/或它们的组合。It should be noted that the terminology used herein is for the purpose of describing specific embodiments only, and is not intended to limit the exemplary embodiments according to the present invention. As used herein, unless the context clearly dictates otherwise, the singular is intended to include the plural as well, furthermore, it is to be understood that when the terms "comprising" and/or "including" are used in this specification, it indicates that There are features, steps, operations, components and/or combinations thereof.
本发明实施例中所用到的原料、试剂均为常规化学产品，均能通过市场购买得到。The raw materials and reagents used in the embodiments of the present invention are all conventional chemical products, which can be purchased from the market.
为了丰富沥青乳化剂的种类，本发明的一种实施方式中，提供了一种含酯基多胺季铵盐型沥青乳化剂，其分子结构通式为：
其中，R为-NH(CH2CH2NH)m-H、
该含酯基多胺季铵盐型沥青乳化剂的结构将羟基、胺基、季铵盐和酯基亲水基团以一定的基团形式有效结合起来，再加之合适的碳链结构和其他亲油基团，共同形成这一新型结构的沥青乳化剂。The structure of the ester-containing polyamine quaternary ammonium salt-type asphalt emulsifier effectively combines hydroxyl, amine, quaternary ammonium and ester hydrophilic groups in a certain group form, together with a suitable carbon chain structure and other The lipophilic groups together form the asphalt emulsifier of this new structure.
本发明的一种实施方式中，提供了一种含酯基多胺季铵盐型沥青乳化剂制备方法，包括以下步骤：In one embodiment of the present invention, there is provided a method for preparing an ester group-containing polyamine quaternary ammonium salt type asphalt emulsifier, comprising the following steps:
(1)将妥尔油脂肪酸、醇类溶剂和环氧氯丙烷混合反应，得到反应中间体I，所述反应中间体I的结构式为
(2)向反应中间体I中再逐渐加入多胺类化合物，混合反应，得到反应中间体II，所述反应中间体II的结构通式为
其中，R为-NH(CH2CH2NH)m-H、
(3)将三甲胺水溶液、盐酸和环氧氯丙烷混合反应，得到反应中间体III；(3) mixed reaction of trimethylamine aqueous solution, hydrochloric acid and epichlorohydrin to obtain reaction intermediate III;
(4)向反应中间体II中再逐渐加入反应中间体III，混合反应，即得到含酯基多胺季铵盐型沥青乳化剂。(4) The reaction intermediate III is gradually added to the reaction intermediate II, and the mixed reaction is performed to obtain an ester group-containing polyamine quaternary ammonium salt type asphalt emulsifier.
在本发明一些优选的实施方式中，妥尔油脂肪酸、醇类溶剂、环氧氯丙烷、多胺类化合物、三甲胺水溶液、盐酸和环氧氯丙烷的摩尔比为1mol：(1.50-4.50)mol：(1.00-1.10)mol：(1.00-1.10)mol：(1.05-1.15)mol：(1.05-1.15)mol：(1.00-1.10)mol。In some preferred embodiments of the present invention, the molar ratio of tall oil fatty acid, alcohol solvent, epichlorohydrin, polyamine compound, trimethylamine aqueous solution, hydrochloric acid and epichlorohydrin is 1 mol: (1.50-4.50) mol: (1.00-1.10) mol: (1.00-1.10) mol: (1.05-1.15) mol: (1.05-1.15) mol: (1.00-1.10) mol.
经过大量实验验证与分析，上述摩尔比例的各原料使得本发明制备得到的含酯基多胺季铵盐型沥青乳化剂的性能较理想，不合适的配比关系的原料不能形成含酯基多胺季铵盐型沥青乳化剂。After a large amount of experimental verification and analysis, the above molar ratios of the raw materials make the performance of the ester group-containing polyamine quaternary ammonium salt type asphalt emulsifier prepared by the present invention ideal, and the raw materials with an inappropriate ratio cannot form an ester group-containing polyamine salt type asphalt emulsifier. Amine quaternary ammonium salt type asphalt emulsifier.
在本发明一些优选的实施方式中，所述妥尔油脂肪酸为针叶树木用硫酸盐法制纸浆的蒸煮废液得到的副产物，其来源广泛，可生物降解，以其作为原料生产沥青乳化剂具有成本低廉等特点。经过大量实验验证与分析，并根据本发明制得的含酯基多胺季铵盐型沥青乳化剂的需要，选择上述妥尔油脂肪酸制得的沥青乳化剂的效果较好。In some preferred embodiments of the present invention, the tall oil fatty acid is a by-product obtained from the cooking waste liquor of coniferous trees using the sulfate method to make pulp, which has a wide range of sources and is biodegradable. Features such as low cost. After a large number of experimental verification and analysis, and according to the requirements of the ester-containing polyamine quaternary ammonium salt type asphalt emulsifier prepared by the present invention, the asphalt emulsifier prepared by selecting the above tall oil fatty acid has a better effect.
在本发明一些优选的实施方式中，所述多胺类化合物为四乙烯五胺、三乙烯四胺、N-氨乙基哌嗪、β-羟乙基乙二胺或二乙烯三胺，经过大量实验验证与分析，并根据本发明制得的含酯基多胺季铵盐型沥青乳化剂的需要，选择上述多胺类化合物制得的沥青乳化剂的效果较好。In some preferred embodiments of the present invention, the polyamine compound is tetraethylenepentamine, triethylenetetramine, N-aminoethylpiperazine, β-hydroxyethylethylenediamine or diethylenetriamine. A large number of experiments are verified and analyzed, and according to the needs of the ester-containing polyamine quaternary ammonium salt type asphalt emulsifier prepared by the present invention, the asphalt emulsifier prepared by selecting the above polyamine compounds has better effect.
在本发明一些优选的实施方式中，所述醇类溶剂为乙醇或异丙醇，经过大量实验验证与分析，并根据本发明制得的含酯基多胺季铵盐型沥青乳化剂的需要，选择上述醇类溶剂制得的沥青乳化剂的效果较好。In some preferred embodiments of the present invention, the alcoholic solvent is ethanol or isopropanol. After a large number of experimental verification and analysis, and according to the needs of the ester-containing polyamine quaternary ammonium salt type asphalt emulsifier prepared by the present invention , the effect of the asphalt emulsifier prepared by selecting the above-mentioned alcohol solvent is better.
在本发明一些优选的实施方式中，步骤(1)中，反应的温度为40-55℃，反应的时间为3-4h。In some preferred embodiments of the present invention, in step (1), the reaction temperature is 40-55° C., and the reaction time is 3-4 h.
在本发明一些优选的实施方式中，步骤(2)中，反应的温度为60-80℃，优选为65-75℃，反应的时间为2-3h。In some preferred embodiments of the present invention, in step (2), the reaction temperature is 60-80° C., preferably 65-75° C., and the reaction time is 2-3 h.
在本发明一些优选的实施方式中，步骤(3)中，反应的温度为45℃，反应的时间为2h。In some preferred embodiments of the present invention, in step (3), the reaction temperature is 45° C., and the reaction time is 2 h.
在本发明一些优选的实施方式中，步骤(4)中，反应的温度为60-80℃，优选为65-75℃，反应的时间为2-3h。In some preferred embodiments of the present invention, in step (4), the reaction temperature is 60-80° C., preferably 65-75° C., and the reaction time is 2-3 h.
在本发明一种较为具体的实施方式中，所述含酯基多胺季铵盐型沥青乳化剂的制备方法，具体包括如下步骤：In a more specific embodiment of the present invention, the preparation method of the ester-containing polyamine quaternary ammonium salt type asphalt emulsifier specifically includes the following steps:
(1)将妥尔油脂肪酸加入到反应容器中，加入醇类溶剂，加热搅拌混合，再分批加入环氧氯丙烷，加入完毕后，在40-55℃搅拌反应3-4h，得到反应中间体I；(1) Add tall oil fatty acid into the reaction vessel, add alcohol solvent, heat and stir to mix, and then add epichlorohydrin in batches. After the addition is complete, stir and react at 40-55° C. for 3-4 hours to obtain a reaction intermediate body I;
(2)向反应中间体I中再逐渐加入多胺类化合物，加入完毕后，在60-80℃反应2-3h，得到反应中间体II；(2) The polyamine compound is gradually added to the reaction intermediate I, and after the addition is completed, the reaction is carried out at 60-80° C. for 2-3 hours to obtain the reaction intermediate II;
(3)将质量分数33％的三甲胺水溶液加入到反应容器中，逐渐加入质量分数30％的工业盐酸，加入完毕后，再逐渐加入环氧氯丙烷，加入完毕后，在45℃搅拌反应2h，得到反应中间体III；(3) Add the trimethylamine aqueous solution with a mass fraction of 33% into the reaction vessel, gradually add a mass fraction of 30% of industrial hydrochloric acid, after the addition is completed, gradually add epichlorohydrin, and after the addition is completed, stir and react at 45 ° C for 2 hours , to obtain reaction intermediate III;
(4)向反应中间体II中再逐渐加入反应中间体III，加入完毕后，在60-80℃反应2-3h，即得到含酯基多胺季铵盐型沥青乳化剂。(4) The reaction intermediate III is gradually added to the reaction intermediate II, and after the addition is completed, the reaction is carried out at 60-80° C. for 2-3 hours to obtain the ester-containing polyamine quaternary ammonium salt type asphalt emulsifier.
本发明的一种实施方式中，提供了上述含酯基多胺季铵盐型沥青乳化剂在制备乳化沥青中的应用。In one embodiment of the present invention, the application of the above-mentioned ester-group-containing polyamine quaternary ammonium salt type asphalt emulsifier in preparing emulsified asphalt is provided.
在本发明一些优选的实施方式中，提供了上述含酯基多胺季铵盐型沥青乳化剂在制备慢裂型阳离子乳化沥青中的应用。In some preferred embodiments of the present invention, the application of the above-mentioned ester-group-containing polyamine quaternary ammonium salt-type asphalt emulsifier in the preparation of slow-cracking cationic emulsified asphalt is provided.
本发明以多胺类化合物作为沥青乳化剂的反应原料，在沥青乳化剂的分子结构中通过加入多胺类化合物引入了胺基，增加了沥青乳化剂的亲水性，以及乳化剂与沥青的相容性。另外，综合考虑碳链长度对于沥青乳化剂的HLB值(亲水/亲油平衡值)和CMC(临界胶束浓度)的影响，选择以妥尔油脂肪酸、环氧氯丙烷和三甲胺作为反应的原料，使制备的沥青乳化剂的HLB值在最佳范围以内，提高了对沥青的乳化性能。The invention uses polyamine compounds as the reaction raw material of the asphalt emulsifier, and introduces amine groups into the molecular structure of the asphalt emulsifier by adding polyamine compounds, thereby increasing the hydrophilicity of the asphalt emulsifier, and the relationship between the emulsifier and the asphalt. compatibility. In addition, considering the influence of carbon chain length on the HLB value (hydrophilic/lipophilic balance) and CMC (critical micelle concentration) of the asphalt emulsifier, tall oil fatty acid, epichlorohydrin and trimethylamine were selected as the reaction The HLB value of the prepared asphalt emulsifier is within the optimal range, and the emulsification performance of the asphalt is improved.
针对本发明中的含酯基多胺季铵盐型沥青乳化剂，本发明的一种实施方式中还提供一种阳离子乳化沥青的制备方法，包括如下步骤：沥青乳化剂的用量为制备的乳化沥青总质量的1.0-3.0％，将上述沥青乳化剂加水配制成水溶液，用工业盐酸调节pH值至2-3，加热至60-70℃，制得皂液；将加热后的沥青和乳化剂皂液通过胶体磨乳化制备出阳离子乳化沥青。For the ester group-containing polyamine quaternary ammonium salt type asphalt emulsifier in the present invention, an embodiment of the present invention also provides a preparation method of cationic emulsified asphalt, comprising the following steps: the amount of the asphalt emulsifier is the amount of the prepared emulsified asphalt. 1.0-3.0% of the total mass of the asphalt, add water to the above-mentioned asphalt emulsifier to prepare an aqueous solution, adjust the pH value to 2-3 with industrial hydrochloric acid, and heat it to 60-70 ° C to prepare soap liquid; the heated asphalt and emulsifier are mixed. The soap solution was emulsified by colloid mill to prepare cationic emulsified asphalt.
本发明的一种实施方式中，提供了上述阳离子乳化沥青的制备方法制备得到的阳离子乳化沥青。In one embodiment of the present invention, a cationic emulsified asphalt prepared by the above-mentioned preparation method of cationic emulsified asphalt is provided.
为了使得本领域技术人员能够更加清楚地了解本发明的技术方案，以下将结合具体的实施例与对比例详细说明本发明的技术方案。In order to enable those skilled in the art to understand the technical solutions of the present invention more clearly, the technical solutions of the present invention will be described in detail below with reference to specific embodiments and comparative examples.
实施例1Example 1
(1)含酯基多胺季铵盐型沥青乳化剂的制备：(1) Preparation of ester-containing polyamine quaternary ammonium salt type asphalt emulsifier:
1)在反应器中加入282.5g妥尔油脂肪酸，100g异丙醇，加热搅拌混合。55℃下逐渐加入95.2g环氧氯丙烷，加完后在55℃搅拌反应3h，得到反应中间体I；1) Add 282.5g tall oil fatty acid and 100g isopropanol into the reactor, heat and stir to mix. 95.2g of epichlorohydrin was gradually added at 55°C, and after the addition was completed, the reaction was stirred at 55°C for 3 hours to obtain the reaction intermediate I;
反应如下：The reaction is as follows:
所合成反应中间体I的红外谱图分析结果如下：3010cm-1为环氧基团C-H和双键C＝C-H的伸缩振动吸收峰的叠加峰，2926cm-1为亚甲基的非对称伸缩振动吸收峰，2856cm-1为亚甲基的对称伸缩振动收峰，1711cm-1为C＝O双键的伸缩振动吸收峰，1648cm-1为C＝C双键伸缩振动吸收峰，1460cm-1为亚甲基的非对称弯曲振动，1411cm-1为甲基的非对称弯曲振动，1285cm-1为环氧基团伸缩振动吸收峰，1096cm-1为C-H的面内弯曲振动吸收峰，935cm-1为环氧基团伸缩振动吸收峰，720cm-1为亚甲基面内摇摆振动吸收峰，无755cm-1附近的C-Cl伸缩振动吸收峰。The infrared spectrum analysis results of the synthesized reaction intermediate I are as follows: 3010 cm -1 is the superposition peak of the stretching vibration absorption peaks of the epoxy group CH and the double bond C=CH, and 2926 cm -1 is the asymmetric stretching vibration of the methylene group Absorption peak, 2856cm -1 is the symmetric stretching vibration absorption peak of methylene group, 1711cm -1 is the stretching vibration absorption peak of the C=O double bond, 1648cm -1 is the C=C double bond stretching vibration absorption peak, 1460cm -1 is the stretching vibration absorption peak of the C=C double bond The asymmetric bending vibration of methylene group, 1411cm -1 is the asymmetric bending vibration of methyl group, 1285cm -1 is the stretching vibration absorption peak of epoxy group, 1096cm -1 is the in-plane bending vibration absorption peak of CH, 935cm -1 Epoxy group stretching vibration absorption peak, 720cm -1 is the methylene in-plane rocking vibration absorption peak, there is no C-Cl stretching vibration absorption peak near 755cm -1 .
2)向反应中间体I中再逐渐加入191.2g四乙烯五胺，加入完毕后，在70℃反应2h，得到反应中间体II；反应如下：2) 191.2g of tetraethylene pentamine was gradually added to the reaction intermediate I, and after the addition was completed, the reaction was carried out at 70° C. for 2 h to obtain the reaction intermediate II; the reaction was as follows:
所合成反应中间体II的红外谱图分析结果如下：3404cm-1为O-H的伸缩振动吸收峰，3268cm-1为N-H的伸缩振动吸收峰，3011cm-1为C＝C-H的伸缩振动吸收峰，2921cm-1为亚甲基的非对称伸缩振动吸收峰，2850cm-1为亚甲基的对称伸缩振动收峰，1735cm-1为C＝O双键的伸缩振动，1639cm-1为C＝C双键伸缩振动吸收峰，1554cm-1为N-H的变形振动吸收峰，1458cm-1为亚甲基的非对称弯曲振动，1400cm-1为甲基的非对称弯曲振动，1309cm-1为C-OH的伸缩振动吸收峰，1108cm-1为C-H的面内弯曲振动吸收峰，922cm-1为C(OH)-H的弯曲振动吸收峰，722cm-1为亚甲基面内摇摆振动吸收峰。The infrared spectrum analysis results of the synthesized reaction intermediate II are as follows: 3404 cm -1 is the stretching vibration absorption peak of OH, 3268 cm -1 is the stretching vibration absorption peak of NH, 3011 cm -1 is the stretching vibration absorption peak of C=CH, 2921 cm -1 is the asymmetric stretching vibration absorption peak of methylene, 2850cm -1 is the symmetric stretching vibration peak of methylene, 1735cm -1 is the stretching vibration of C=O double bond, 1639cm -1 is C=C double bond Stretching vibration absorption peak, 1554cm -1 is the deformation vibration absorption peak of NH, 1458cm -1 is the asymmetric bending vibration of methylene, 1400cm -1 is the asymmetric bending vibration of methyl, 1309cm -1 is the stretching vibration of C-OH Vibration absorption peaks, 1108 cm -1 is the in-plane bending vibration absorption peak of CH, 922 cm -1 is the bending vibration absorption peak of C(OH)-H, and 722 cm -1 is the in-plane rocking vibration absorption peak of methylene.
3)在另一反应器中加入193.1g三甲胺水溶液(质量分数33％)，逐渐加入131.2g工业盐酸(质量分数30％)，再逐渐加入97.1g环氧氯丙烷，加完后在45℃搅拌反应2h，得到反应中间体III；3) In another reactor, add 193.1g trimethylamine aqueous solution (mass fraction 33%), gradually add 131.2g industrial hydrochloric acid (mass fraction 30%), then gradually add 97.1g epichlorohydrin, after adding, at 45 ℃ The reaction was stirred for 2h to obtain the reaction intermediate III;
反应如下：The reaction is as follows:
4)向反应中间体II中再逐渐加入反应中间体III，加入完毕后，在70℃反应2h，即得到含酯基多胺季铵盐型沥青乳化剂，留作乳化沥青试验；4) To the reaction intermediate II, gradually add the reaction intermediate III, and after the addition, react at 70° C. for 2 hours to obtain the ester-group-containing polyamine quaternary ammonium salt type asphalt emulsifier, which is reserved for the emulsified asphalt test;
反应如下：The reaction is as follows:
所合成产物含酯基多胺季铵盐型沥青乳化剂的红外谱图分析结果如下：3416cm-1为O-H的伸缩振动吸收峰，3262cm-1为N-H的伸缩振动吸收峰，2926cm-1为亚甲基的非对称伸缩振动吸收峰，2856cm-1为亚甲基的对称伸缩振动收峰，1718cm-1为C＝O双键的伸缩振动吸收峰，1642cm-1为C＝C双键的伸缩振动吸收峰，1551cm-1为N-H的变形振动吸收峰，1474cm-1为亚甲基的非对称弯曲振动，1411cm-1为甲基的非对称弯曲振动，1300cm-1为C-OH的伸缩振动吸收峰，1096cm-1为C-H的面内弯曲振动吸收峰，963cm-1为C(OH)-H的弯曲振动吸收峰，916cm-1为亚甲基面外弯曲振动吸收峰，713cm-1为亚甲基面内摇摆振动吸收峰。The results of infrared spectrogram analysis of the synthesized product-containing polyamine quaternary ammonium salt type asphalt emulsifier are as follows: 3416cm -1 is the stretching vibration absorption peak of OH, 3262cm -1 is the stretching vibration absorption peak of NH, and 2926cm -1 is the sub The asymmetric stretching vibration absorption peak of methyl group, 2856 cm -1 is the symmetrical stretching vibration absorption peak of methylene group, 1718 cm -1 is the stretching vibration absorption peak of C=O double bond, 1642 cm -1 is the stretching vibration absorption peak of C=C double bond Vibrational absorption peaks, 1551cm -1 is the deformation vibration absorption peak of NH, 1474cm -1 is the asymmetric bending vibration of methylene, 1411cm -1 is the asymmetric bending vibration of methyl, 1300cm -1 is the stretching vibration of C-OH Absorption peaks, 1096 cm -1 is the in-plane bending vibration absorption peak of CH, 963 cm -1 is the bending vibration absorption peak of C(OH)-H, 916 cm -1 is the out-of-plane bending vibration absorption peak of methylene, and 713 cm -1 is the bending vibration absorption peak of methylene The in-plane rocking vibration absorption peak of methylene.
(2)乳化沥青的制备：(2) Preparation of emulsified asphalt:
取AH-90#沥青300g，加热至125℃，将10.0g本实施例制备的沥青乳化剂加入到200g水中，用工业盐酸调节pH值至2-3，加热至65℃，制得皂液。将沥青和乳化剂皂液通过胶体磨乳化制备出阳离子型乳化沥青。Take 300g of AH-90# asphalt, heat it to 125°C, add 10.0g of the asphalt emulsifier prepared in this example to 200g of water, adjust the pH value to 2-3 with industrial hydrochloric acid, and heat to 65°C to obtain a soap solution. The cationic emulsified asphalt was prepared by emulsification of asphalt and emulsifier soap by colloid mill.
(3)乳化沥青性能检测：(3) Performance testing of emulsified asphalt:
制得的乳化沥青按中国交通部制订的阳离子乳化沥青行业标准(JTJ052-2000)进行检测，结果如下：本实施例制备的乳化沥青均匀、细腻，沥青含量为56％，筛上剩余量为0.04％，与矿料裹覆面积大于2/3，电荷为阳离子；采用拌和料进行拌和并加SBR改性胶乳，其可拌和时间大于2分钟。表明该乳化剂制备的沥青乳液为慢裂型阳离子乳化沥青，沥青乳化剂为慢裂型。The obtained emulsified asphalt is tested according to the industry standard of cationic emulsified asphalt (JTJ052-2000) formulated by the Ministry of Communications of China, and the results are as follows: The emulsified asphalt prepared in this example is uniform and fine, the asphalt content is 56%, and the remaining amount on the sieve is 0.04 %, the coverage area with the mineral material is more than 2/3, and the charge is cationic; the mixing material is used for mixing and SBR modified latex is added, and the mixing time is more than 2 minutes. It shows that the asphalt emulsion prepared by this emulsifier is slow-cracked cationic emulsified asphalt, and the asphalt emulsifier is of slow-crack type.
实施例2Example 2
(1)含酯基多胺季铵盐型沥青乳化剂的制备：(1) Preparation of ester-containing polyamine quaternary ammonium salt type asphalt emulsifier:
1)在反应器中加入282.5g妥尔油脂肪酸，100g异丙醇，加热搅拌混合。50℃下逐渐加入95.2g环氧氯丙烷，加完后在50℃搅拌反应4h，得到反应中间体I；1) Add 282.5g tall oil fatty acid and 100g isopropanol into the reactor, heat and stir to mix. 95.2g of epichlorohydrin was gradually added at 50°C, and after the addition, the reaction was stirred at 50°C for 4 hours to obtain the reaction intermediate I;
反应如下：The reaction is as follows:
2)向反应中间体I中再逐渐加入147.7g三乙烯四胺，加入完毕后，在65℃反应3h，得到反应中间体II；2) 147.7g of triethylenetetramine was gradually added to the reaction intermediate I, and after the addition was completed, the reaction was carried out at 65° C. for 3 hours to obtain the reaction intermediate II;
反应如下：The reaction is as follows:
3)在另一反应器中加入193.1g三甲胺水溶液(质量分数33％)，逐渐加入131.2g工业盐酸(质量分数30％)，再逐渐加入97.1g环氧氯丙烷，加完后在45℃搅拌反应2h，得到反应中间体III；3) In another reactor, add 193.1g trimethylamine aqueous solution (mass fraction 33%), gradually add 131.2g industrial hydrochloric acid (mass fraction 30%), then gradually add 97.1g epichlorohydrin, after adding, at 45 ℃ The reaction was stirred for 2h to obtain the reaction intermediate III;
反应如下：The reaction is as follows:
4)向反应中间体II中再逐渐加入反应中间体III，加入完毕后，在65℃反应3h，即得到含酯基多胺季铵盐型沥青乳化剂，留作乳化沥青试验。4) To the reaction intermediate II, gradually add the reaction intermediate III. After the addition is completed, react at 65° C. for 3 hours to obtain an ester group-containing polyamine quaternary ammonium salt type asphalt emulsifier, which is reserved for the emulsified asphalt test.
反应如下：The reaction is as follows:
(2)乳化沥青的制备：(2) Preparation of emulsified asphalt:
取AH-90#沥青300g，加热至125℃，将10.0g本实施例制备的沥青乳化剂加入到200g水中，用工业盐酸调节pH值至2-3，加热至65℃，制得皂液。将沥青和乳化剂皂液通过胶体磨乳化制备出阳离子型乳化沥青。Take 300g of AH-90# asphalt, heat it to 125°C, add 10.0g of the asphalt emulsifier prepared in this example to 200g of water, adjust the pH value to 2-3 with industrial hydrochloric acid, and heat to 65°C to obtain a soap solution. The cationic emulsified asphalt was prepared by emulsification of asphalt and emulsifier soap by colloid mill.
(3)乳化沥青性能检测：(3) Performance testing of emulsified asphalt:
制得的乳化沥青按中国交通部制订的阳离子乳化沥青行业标准(JTJ052-2000)进行检测，结果如下：本实施例制备的乳化沥青均匀、细腻，沥青含量为55％，筛上剩余量为0.05％，与矿料裹覆面积大于2/3，电荷为阳离子；采用拌和料进行拌和并加SBR改性胶乳，其可拌和时间大于2分钟。表明该乳化剂制备的沥青乳液为慢裂型阳离子乳化沥青，沥青乳化剂为慢裂型。The obtained emulsified asphalt is tested according to the industry standard of cationic emulsified asphalt (JTJ052-2000) formulated by the Ministry of Communications of China, and the results are as follows: The emulsified asphalt prepared in this example is uniform and fine, the asphalt content is 55%, and the remaining amount on the sieve is 0.05 %, the coverage area with the mineral material is more than 2/3, and the charge is cationic; the mixing material is used for mixing and SBR modified latex is added, and the mixing time is more than 2 minutes. It shows that the asphalt emulsion prepared by this emulsifier is slow-cracked cationic emulsified asphalt, and the asphalt emulsifier is of slow-crack type.
实施例3Example 3
(1)含酯基多胺季铵盐型沥青乳化剂的制备：(1) Preparation of ester-containing polyamine quaternary ammonium salt type asphalt emulsifier:
1)在反应器中加入282.5g妥尔油脂肪酸，100g异丙醇，加热搅拌混合。55℃下逐渐加入95.2g环氧氯丙烷，加完后在55℃搅拌反应3h，得到反应中间体I；1) Add 282.5g tall oil fatty acid and 100g isopropanol into the reactor, heat and stir to mix. 95.2g of epichlorohydrin was gradually added at 55°C, and after the addition was completed, the reaction was stirred at 55°C for 3 hours to obtain the reaction intermediate I;
反应如下：The reaction is as follows:
2)向反应中间体I中再逐渐加入130.3g氨乙基哌嗪，加入完毕后，在70℃反应2h，得到反应中间体II；2) 130.3 g of aminoethylpiperazine was gradually added to the reaction intermediate I, and after the addition was completed, the reaction was carried out at 70° C. for 2 h to obtain the reaction intermediate II;
反应如下：The reaction is as follows:
3)在另一反应器中加入193.1g三甲胺水溶液(质量分数33％)，逐渐加入131.2g工业盐酸(质量分数30％)，再逐渐加入97.1g环氧氯丙烷，加完后在45℃搅拌反应2h，得到反应中间体III；3) In another reactor, add 193.1g trimethylamine aqueous solution (mass fraction 33%), gradually add 131.2g industrial hydrochloric acid (mass fraction 30%), then gradually add 97.1g epichlorohydrin, after adding, at 45 ℃ The reaction was stirred for 2h to obtain the reaction intermediate III;
反应如下：The reaction is as follows:
4)向反应中间体II中再逐渐加入反应中间体III，加入完毕后，在70℃反应2h，即得到含酯基多胺季铵盐型沥青乳化剂，留作乳化沥青试验。4) To the reaction intermediate II, gradually add the reaction intermediate III. After the addition is completed, react at 70° C. for 2 h to obtain the ester-containing polyamine quaternary ammonium salt type asphalt emulsifier, which is reserved for the emulsified asphalt test.
反应如下：The reaction is as follows:
(2)乳化沥青的制备：(2) Preparation of emulsified asphalt:
取AH-70#沥青300g，加热至125℃，将10.0g本实施例制备的沥青乳化剂加入到200g水中，用工业盐酸调节pH值至2-3，加热至65℃，制得皂液。将沥青和乳化剂皂液通过胶体磨乳化制备出阳离子型乳化沥青。Take 300g of AH-70# asphalt, heat it to 125°C, add 10.0g of the asphalt emulsifier prepared in this example to 200g of water, adjust the pH value to 2-3 with industrial hydrochloric acid, and heat to 65°C to obtain a soap solution. The cationic emulsified asphalt was prepared by emulsification of asphalt and emulsifier soap by colloid mill.
(3)乳化沥青性能检测：(3) Performance testing of emulsified asphalt:
制得的乳化沥青按中国交通部制订的阳离子乳化沥青行业标准(JTJ052-2000)进行检测，结果如下：本实施例制备的乳化沥青均匀、细腻，沥青含量为55％，筛上剩余量为0.04％，与矿料裹覆面积大于2/3，电荷为阳离子；采用拌和料进行拌和并加SBR改性胶乳，其可拌和时间大于2分钟。表明该乳化剂制备的沥青乳液为慢裂型阳离子乳化沥青，沥青乳化剂为慢裂型。The obtained emulsified asphalt is tested according to the industry standard of cationic emulsified asphalt (JTJ052-2000) formulated by the Ministry of Communications of China, and the results are as follows: The emulsified asphalt prepared in this example is uniform and fine, the asphalt content is 55%, and the remaining amount on the sieve is 0.04 %, the coverage area with the mineral material is more than 2/3, and the charge is cationic; the mixing material is used for mixing and SBR modified latex is added, and the mixing time is more than 2 minutes. It shows that the asphalt emulsion prepared by this emulsifier is slow-cracked cationic emulsified asphalt, and the asphalt emulsifier is of slow-crack type.
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.
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