CN117049814B - Preparation method of concrete air entraining agent - Google Patents
Preparation method of concrete air entraining agent Download PDFInfo
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- CN117049814B CN117049814B CN202311025018.2A CN202311025018A CN117049814B CN 117049814 B CN117049814 B CN 117049814B CN 202311025018 A CN202311025018 A CN 202311025018A CN 117049814 B CN117049814 B CN 117049814B
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- cellulose ether
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- entraining agent
- concrete air
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- 239000004567 concrete Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 107
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 103
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 103
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 72
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229920003086 cellulose ether Polymers 0.000 claims abstract description 33
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 26
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 235000019832 sodium triphosphate Nutrition 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 12
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims abstract description 10
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims abstract description 10
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims abstract description 10
- -1 methyl hydroxypropyl Chemical group 0.000 claims abstract description 10
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 46
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 20
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 18
- 238000009835 boiling Methods 0.000 claims description 14
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 12
- 230000003197 catalytic effect Effects 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 9
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 6
- 230000003213 activating effect Effects 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 6
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 6
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 6
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 6
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 4
- 239000004566 building material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003921 oil Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000010754 BS 2869 Class F Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002969 artificial stone Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/304—Air-entrainers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Abstract
The invention discloses a preparation method of a concrete air entraining agent, and relates to the technical field of building materials. When the concrete air entraining agent is prepared, firstly, rosin powder and epoxy chloropropane are reacted to prepare pretreated rosin; dehydrochlorinating the pretreated rosin under alkaline conditions to obtain active rosin; reacting methyl hydroxypropyl cellulose ether with active rosin to prepare rosin-based cellulose ether; pure water, sodium hydroxide, rosin-based cellulose ether, sodium tripolyphosphate and triethanolamine are mixed to form the concrete air entraining agent. The concrete air entraining agent prepared by the invention has good stability and use effect.
Description
Technical Field
The invention relates to the technical field of building materials, in particular to a preparation method of a concrete air entraining agent.
Background
Concrete is one of the most prominent civil engineering materials in the current generation. The artificial stone is prepared from cementing material, granular aggregate (also called aggregate), water, and additives and admixtures added if necessary according to a certain proportion through uniformly stirring, compacting, shaping, curing and hardening. The concrete has the characteristics of rich raw materials, low price and simple production process, so that the consumption of the concrete is increased. Meanwhile, the concrete has the characteristics of high compressive strength, good durability, wide strength grade range and the like. The characteristics lead the application range to be very wide, and the concrete is not only used in various civil engineering, namely shipbuilding industry, mechanical industry, ocean development, geothermal engineering and the like, but also is an important material. In cold areas, as the concrete has a plurality of pores, the concrete has weak impermeability and serious water inflow under the conventional environment, and has high heat conductivity, and the high-frequency freezing and thawing can cause the deterioration and damage of the concrete structure, thereby influencing the service life; and a proper amount of bubbles with reasonable size and structure are filled in the concrete, so that the frost resistance and durability of the concrete are greatly improved.
The addition of air entraining agent to concrete is an effective way to improve the impermeability, frost resistance, durability and crack resistance. In the prior art, the super-doped air entraining agent is used as a technical means, and the initial air content is improved to ensure that the air content reaches the standard in the later pouring process. However, the method can seriously reduce the workability of the concrete, and the size of the air bubble content of the concrete has larger randomness, so that the strength, the durability and the mechanical property stability of the concrete can be influenced. Therefore, there is a need to develop an air entraining agent with strong bubble stability.
Disclosure of Invention
The invention aims to provide a preparation method of a concrete air entraining agent, which aims to solve the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
the preparation method of the concrete air entraining agent comprises the following preparation steps:
(1) Reacting rosin powder with epoxy chloropropane to obtain pretreated rosin;
(2) Dehydrochlorinating the pretreated rosin under alkaline conditions to obtain active rosin;
(3) Reacting methyl hydroxypropyl cellulose ether with active rosin to prepare rosin-based cellulose ether;
(4) Pure water, sodium hydroxide, rosin-based cellulose ether, sodium tripolyphosphate and triethanolamine are mixed to form the concrete air entraining agent.
Further, the preparation method comprises the following preparation steps:
(1) Pretreatment: uniformly mixing rosin powder, epichlorohydrin, tetrabutylammonium bromide and 1, 2-dichloroethane according to the mass ratio of 1:1:0.1-0.2:3-4, stirring and reacting for 6-8 hours at 70-80 ℃ at 300-500 r/min in a nitrogen atmosphere, and standing for 8-10 hours at 10-20 ℃ at 10-50 Pa to obtain pretreated rosin;
(2) Activating: adding 1, 2-dichloroethane 3-4 times of the pretreated rosin into the pretreated rosin, adding sodium hydroxide aqueous solution 40% of the mass fraction of the pretreated rosin 4-6 times of the pretreated rosin, stirring at 30-40 ℃ for reaction for 4-6 hours at 300-500 r/min, regulating the pH to be neutral by supersaturated saline, separating liquid to obtain an oil phase, and standing at 10-20 ℃ at 10-50 Pa for 8-10 hours to obtain active rosin;
(3) Preparation of rosin-based cellulose ether: uniformly mixing hydroxypropyl methyl cellulose ether, active rosin and dimethyl sulfoxide according to the mass ratio of 1:1:30-40, adding catalytic liquid which is 1-2 times of the mass of the methyl hydroxypropyl cellulose ether at a constant speed in 6-8 min under the stirring condition of 60-70 ℃ and 300-500 r/min in a nitrogen atmosphere, continuously stirring and reacting for 30-40 min, standing for 8-10 h at 10-20 ℃ and 10-50 Pa, washing for 3-5 times by pure water, and drying for 6-8 h at 60-70 ℃ to obtain rosin-based cellulose ether;
(4) Preparation of a concrete air entraining agent: heating pure water to boiling, adding sodium hydroxide into the pure water in a nitrogen atmosphere, stirring for 20-30 min at 300-500 r/min in the boiling state, adding rosin-based cellulose ether and sodium tripolyphosphate aqueous solution with mass concentration of 2% -3%, continuously stirring for 10-15 min, cooling to 30-40 ℃, adding triethanolamine, continuously stirring for 30-40 min, and standing for 6-8 h to obtain the concrete air entraining agent.
Further, the pretreatment rosin in the step (1) is prepared from resin acid in rosin powder, fatty acid and epichlorohydrin, and the following reaction process is adopted as an example of abietic acid in the resin acid:
further, the reaction process of the active rosin in the step (2) is that the pretreated abietic acid is as follows:
further, the reaction process of the rosin-based cellulose ether in the step (3) is carried out by using activated abietic acid as follows:
wherein R is H, CH 3 、CH 2 CH(OH)CH 3 One of the following;
R 1 is that
R 2 R, R of a shape of R, R 1 Or (b)
Further, the catalytic liquid in the step (3) is prepared by uniformly mixing tin tetrachloride and dimethyl sulfoxide according to the mass ratio of 1:18-22.
Further, the concrete air entraining agent in the step (4) comprises the following components in parts by weight: 100 to 120 parts of pure water, 2.5 to 3.5 parts of sodium hydroxide, 4 to 6 parts of rosin-based cellulose ether, 1 to 2 parts of sodium tripolyphosphate aqueous solution with the mass concentration of 2 to 3 percent and 5 to 15 parts of triethanolamine.
Further, the concrete air entraining agent in the step (4) is concentrated solution, and can be diluted according to engineering use conditions.
Compared with the prior art, the invention has the following beneficial effects:
the concrete air entraining agent prepared by the invention firstly reacts rosin powder with epoxy chloropropane to prepare pretreated rosin; dehydrochlorinating the pretreated rosin under alkaline conditions to obtain active rosin; reacting methyl hydroxypropyl cellulose ether with active rosin to prepare rosin-based cellulose ether; pure water, sodium hydroxide, rosin-based cellulose ether, sodium tripolyphosphate and triethanolamine are mixed to form the concrete air entraining agent.
Firstly, the invention synthesizes the amphiphilic high molecular compound which takes rosin as lipophilic group and cellulose sugar unit as hydrophilic group by taking natural renewable resources as basic raw materials through grafting modification design, has good air entraining effect when being used in concrete, and ensures that the amphiphilic high molecular compound has better stability at an air-water interface. The raw materials are extracted from plants, so that the additional value of agriculture and forestry is improved, the dependence of the existing amphiphilic polymer compounds on petrochemical resources is reduced, the production and application of the amphiphilic polymer compounds are more in accordance with the environmental protection and green development requirements, the problems of serious environmental pollution, poor performance, high cost, difficult degradation and the like of the traditional surfactant are solved, a way is provided for the advanced processing and utilization of rosin and cellulose, the application field is widened, and the potential application value is improved.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In order to more clearly illustrate the method provided by the invention, the following examples are used for describing the concrete air entraining agent in detail, and the method for testing each index of the concrete air entraining agent prepared in the following examples is as follows:
stability: the concrete air entraining agent obtained in each example and the concrete air entraining agent obtained in the comparative example are mixed with pure water according to the mass ratio of 1:99, and phenomena such as precipitation delamination are observed.
The using effect is as follows: the concrete air entraining agent obtained in each example and comparative example is prepared by mixing cement: fly ash: sand: stone: water: concrete air entraining agent = 210:490:857:766:105:22, wherein the cement adopts natural sand and pebbles produced by a P.042.5 cement large Dan Xia natural aggregate processing system produced by Achillea-Duoblate cement Co., ltd., and the three-stage matched normal concrete aggregate combination adopts small stones: medium stone: marble=30: 30:40, a step of performing a; class F II fly ash produced by Akesu thermoelectric Co., ltd., and used for compressive strength detection
Example 1
The preparation method of the concrete air entraining agent comprises the following preparation steps:
(1) Pretreatment: uniformly mixing rosin powder, epichlorohydrin, tetrabutylammonium bromide and 1, 2-dichloroethane according to a mass ratio of 1:1:0.1:3, stirring and reacting for 6 hours at 70 ℃ at 300r/min in a nitrogen atmosphere, and standing for 8 hours at 10 ℃ at 10Pa to obtain pretreated rosin;
(2) Activating: adding 1, 2-dichloroethane 3 times of the pretreated rosin into the pretreated rosin, adding sodium hydroxide aqueous solution 40% of the mass fraction 4 times of the pretreated rosin, stirring at 30 ℃ for reaction for 4 hours at 300r/min, regulating pH to neutrality with supersaturated saline, separating liquid to obtain an oil phase, and standing at 10 ℃ and 10Pa for 8 hours to obtain active rosin;
(3) Preparation of rosin-based cellulose ether: uniformly mixing tin tetrachloride and dimethyl sulfoxide according to a mass ratio of 1:18 to prepare a catalytic liquid; uniformly mixing hydroxypropyl methyl cellulose ether, active rosin and dimethyl sulfoxide according to a mass ratio of 1:1:30, adding catalytic liquid which is 1 time of the mass of the methyl hydroxypropyl cellulose ether at a constant speed within 6 minutes under the stirring condition of 60 ℃ and 300r/min in a nitrogen atmosphere, continuously stirring and reacting for 30 minutes, standing for 8 hours at 10 ℃ and 10Pa, washing for 3 times with pure water, and drying for 8 hours at 60 ℃ to obtain rosin-based cellulose ether;
(4) Preparation of a concrete air entraining agent: 100 parts of pure water, 2.5 parts of sodium hydroxide, 4 parts of rosin-based cellulose ether, 1 part of sodium tripolyphosphate aqueous solution with the mass concentration of 2% and 5 parts of triethanolamine are taken according to parts by mass for standby; heating pure water to boiling, adding sodium hydroxide into the pure water in a nitrogen atmosphere, stirring for 20min at 300r/min in a boiling state, adding rosin-based cellulose ether and sodium tripolyphosphate aqueous solution with mass concentration of 2% and continuously stirring for 10min, cooling to 30 ℃, adding triethanolamine, continuously stirring for 30min, and standing for 6h to obtain the concrete air entraining agent.
Example 2
The preparation method of the concrete air entraining agent comprises the following preparation steps:
(1) Pretreatment: uniformly mixing rosin powder, epichlorohydrin, tetrabutylammonium bromide and 1, 2-dichloroethane according to the mass ratio of 1:1:0.15:3.5, stirring and reacting for 7h at 75 ℃ and 400r/min in a nitrogen atmosphere, and standing for 9h at 15 ℃ and 30Pa to obtain pretreated rosin;
(2) Activating: adding 1, 2-dichloroethane 3.5 times of the pretreated rosin into the pretreated rosin, adding sodium hydroxide aqueous solution 40% of the mass fraction 5 times of the pretreated rosin, stirring at 35 ℃ and 400r/min for reaction for 5 hours, regulating pH to neutrality with supersaturated saline, separating liquid to obtain an oil phase, and standing at 15 ℃ and 30Pa for 9 hours to obtain active rosin;
(3) Preparation of rosin-based cellulose ether: uniformly mixing tin tetrachloride and dimethyl sulfoxide according to a mass ratio of 1:20 to prepare a catalytic liquid; uniformly mixing hydroxypropyl methyl cellulose ether, active rosin and dimethyl sulfoxide according to a mass ratio of 1:1:35, adding catalytic liquid which is 1.5 times of the mass of the methyl hydroxypropyl cellulose ether at uniform speed in 7min under the stirring condition of 400r/min at the temperature of 65 ℃ in a nitrogen atmosphere, continuously stirring and reacting for 35min, standing for 9h at the temperature of 15 ℃ under the pressure of 30Pa, washing for 4 times with pure water, and drying for 7h at the temperature of 65 ℃ to obtain rosin-based cellulose ether;
(4) Preparation of a concrete air entraining agent: 110 parts of pure water, 3 parts of sodium hydroxide, 5 parts of rosin-based cellulose ether, 1.5 parts of sodium tripolyphosphate aqueous solution with the mass concentration of 2.5% and 10 parts of triethanolamine are taken according to parts by mass for standby; heating pure water to boiling, adding sodium hydroxide into the pure water in a nitrogen atmosphere, stirring for 25min at 400r/min in a boiling state, adding rosin-based cellulose ether and sodium tripolyphosphate aqueous solution with mass concentration of 2.5%, continuously stirring for 12.5min, cooling to 35 ℃, adding triethanolamine, continuously stirring for 35min, and standing for 7h to obtain the concrete air entraining agent.
Example 3
The preparation method of the concrete air entraining agent is characterized by comprising the following preparation steps:
(1) Pretreatment: uniformly mixing rosin powder, epichlorohydrin, tetrabutylammonium bromide and 1, 2-dichloroethane according to a mass ratio of 1:1:0.2:4, stirring and reacting for 8 hours at 80 ℃ at 500r/min in a nitrogen atmosphere, and standing for 10 hours at 20 ℃ at 50Pa to obtain pretreated rosin;
(2) Activating: adding 1, 2-dichloroethane 4 times of the pretreated rosin into the pretreated rosin, adding sodium hydroxide aqueous solution with the mass fraction of 40% and the mass fraction of 6 times of the pretreated rosin, stirring at 40 ℃ for reaction for 6 hours at 500r/min, regulating the pH value to be neutral by supersaturated saline, separating liquid to obtain an oil phase, and standing at 20 ℃ and 50Pa for 10 hours to obtain active rosin;
(3) Preparation of rosin-based cellulose ether: uniformly mixing tin tetrachloride and dimethyl sulfoxide according to a mass ratio of 1:22 to prepare a catalytic liquid; uniformly mixing hydroxypropyl methyl cellulose ether, active rosin and dimethyl sulfoxide according to a mass ratio of 1:1:40, adding catalytic liquid which is 2 times of the mass of the methyl hydroxypropyl cellulose ether at a constant speed within 8min under the stirring condition of 70 ℃ and 500r/min in a nitrogen atmosphere, continuously stirring and reacting for 40min, standing for 10h at 20 ℃ and 50Pa, washing for 5 times with pure water, and drying for 6h at 70 ℃ to obtain rosin-based cellulose ether;
(4) Preparation of a concrete air entraining agent: 120 parts of pure water, 3.5 parts of sodium hydroxide, 6 parts of rosin-based cellulose ether, 2 parts of sodium tripolyphosphate aqueous solution with the mass concentration of 3% and 15 parts of triethanolamine are taken according to parts by mass for standby; heating pure water to boiling, adding sodium hydroxide into the pure water in a nitrogen atmosphere, stirring for 30min at 500r/min in a boiling state, adding rosin-based cellulose ether and 3% sodium tripolyphosphate aqueous solution by mass concentration, continuously stirring for 15min, cooling to 40 ℃, adding triethanolamine, continuously stirring for 40min, and standing for 8h to obtain the concrete air entraining agent.
Comparative example 1
The preparation method of the concrete air entraining agent comprises the following preparation steps:
(1) Pretreatment: uniformly mixing rosin powder, epichlorohydrin, tetrabutylammonium bromide and 1, 2-dichloroethane according to the mass ratio of 1:1:0.15:3.5, stirring and reacting for 7h at 75 ℃ and 400r/min in a nitrogen atmosphere, and standing for 9h at 15 ℃ and 30Pa to obtain pretreated rosin;
(2) Activating: adding 1, 2-dichloroethane 3.5 times of the pretreated rosin into the pretreated rosin, adding sodium hydroxide aqueous solution 40% of the mass fraction 5 times of the pretreated rosin, stirring at 35 ℃ and 400r/min for reaction for 5 hours, regulating pH to neutrality with supersaturated saline, separating liquid to obtain an oil phase, and standing at 15 ℃ and 30Pa for 9 hours to obtain active rosin;
(3) Preparation of a concrete air entraining agent: 110 parts of pure water, 3 parts of sodium hydroxide, 5 parts of active rosin, 1.5 parts of sodium tripolyphosphate aqueous solution with the mass concentration of 2.5% and 10 parts of triethanolamine are taken according to parts by mass for standby; heating pure water to boiling, adding sodium hydroxide into the pure water in a nitrogen atmosphere, stirring for 25min at 400r/min in a boiling state, adding active rosin and a sodium tripolyphosphate aqueous solution with the mass concentration of 2.5% and continuously stirring for 12.5min, cooling to 35 ℃, adding triethanolamine, continuously stirring for 35min, and standing for 7h to obtain the concrete air entraining agent.
Comparative example 2
The preparation method of the concrete air entraining agent comprises the following preparation steps:
(1) Preparation of rosin-based cellulose ether: uniformly mixing tin tetrachloride and dimethyl sulfoxide according to a mass ratio of 1:20 to prepare a catalytic liquid; uniformly mixing hydroxypropyl methyl cellulose ether, rosin powder and dimethyl sulfoxide according to a mass ratio of 1:1:35, adding catalytic liquid which is 1.5 times of the mass of the methyl hydroxypropyl cellulose ether at uniform speed within 7min under the stirring condition of 400r/min at 65 ℃ in a nitrogen atmosphere, continuously stirring and reacting for 35min, standing for 9h at 15 ℃ under 30Pa, washing for 4 times with pure water, and drying for 7h at 65 ℃ to obtain rosin-based cellulose ether;
(2) Preparation of a concrete air entraining agent: 110 parts of pure water, 3 parts of sodium hydroxide, 5 parts of rosin-based cellulose ether, 1.5 parts of sodium tripolyphosphate aqueous solution with the mass concentration of 2.5% and 10 parts of triethanolamine are taken according to parts by mass for standby; heating pure water to boiling, adding sodium hydroxide into the pure water in a nitrogen atmosphere, stirring for 25min at 400r/min in a boiling state, adding rosin-based cellulose ether and sodium tripolyphosphate aqueous solution with mass concentration of 2.5%, continuously stirring for 12.5min, cooling to 35 ℃, adding triethanolamine, continuously stirring for 35min, and standing for 7h to obtain the concrete air entraining agent.
Effect example
The following table 1 shows the results of analysis of the stability of the concrete air entraining agents prepared using examples 1 to 3 according to the invention and comparative examples 1 to 2.
TABLE 1
From Table 1, it can be seen that the concrete air entraining agents prepared in examples 1,2, 3 have good stability.
The following Table 2 shows the results of analysis of the stability of the concrete air entraining agents prepared by examples 1 to 3 according to the invention and comparative examples 1 to 2.
TABLE 2
From Table 2, it can be seen that the concrete air entraining agents prepared in examples 1,2, 3 have good use results.
Table 3 below shows the results of the test carried out by the group experimental test company Ge Zhou in example 2 of the present invention, as follows:
TABLE 3 Table 3
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (3)
1. The preparation method of the concrete air entraining agent is characterized by comprising the following preparation steps:
(1) Reacting rosin powder with epoxy chloropropane to obtain pretreated rosin;
(2) Dehydrochlorinating the pretreated rosin under alkaline conditions to obtain active rosin;
(3) Reacting methyl hydroxypropyl cellulose ether with active rosin to prepare rosin-based cellulose ether;
(4) Mixing pure water, sodium hydroxide, rosin-based cellulose ether, sodium tripolyphosphate and triethanolamine to form a concrete air entraining agent;
the preparation method specifically comprises the following preparation steps:
(1) Pretreatment: uniformly mixing rosin powder, epichlorohydrin, tetrabutylammonium bromide and 1, 2-dichloroethane according to a mass ratio of 1:1:0.1-0.2:3-4, stirring and reacting for 6-8 hours at 70-80 ℃ and 300-500 r/min in a nitrogen atmosphere, and standing for 8-10 hours at 10-20 ℃ and 10-50 Pa to obtain pretreated rosin;
(2) Activating: adding 1, 2-dichloroethane 3-4 times of the mass of the pretreated rosin into the pretreated rosin, adding a sodium hydroxide aqueous solution with the mass fraction of 40% and 4-6 times of the mass of the pretreated rosin, stirring at 30-40 ℃ for reaction for 4-6 hours at 300-500 r/min, regulating the pH to be neutral by supersaturated saline, separating liquid to obtain an oil phase, and standing at 10-20 ℃ for 8-10 hours at 10-50 Pa to obtain active rosin;
(3) Preparation of rosin-based cellulose ether: uniformly mixing hydroxypropyl methyl cellulose ether, active rosin and dimethyl sulfoxide according to a mass ratio of 1:1:30-40, adding catalytic liquid which is 1-2 times of the mass of the methyl hydroxypropyl cellulose ether at a constant speed in 6-8 min under the stirring condition of 60-70 ℃ and 300-500 r/min in a nitrogen atmosphere, continuously stirring and reacting for 30-40 min, standing for 8-10 h at 10-20 ℃ and 10-50 Pa, washing for 3-5 times by pure water, and drying for 6-8 h at 60-70 ℃ to obtain rosin-based cellulose ether;
(4) Preparation of a concrete air entraining agent: heating pure water to boiling, adding sodium hydroxide into the pure water in a nitrogen atmosphere, stirring for 20-30 min at 300-500 r/min in a boiling state, adding rosin-based cellulose ether and sodium tripolyphosphate aqueous solution with mass concentration of 2% -3% and continuously stirring for 10-15 min, cooling to 30-40 ℃, adding triethanolamine, continuously stirring for 30-40 min, and standing for 6-8 h to obtain the concrete air entraining agent.
2. The preparation method of the concrete air entraining agent according to claim 1 is characterized in that the catalytic liquid in the step (3) is prepared by uniformly mixing tin tetrachloride and dimethyl sulfoxide according to a mass ratio of 1:18-22.
3. The method for preparing the concrete air entraining agent according to claim 1, wherein the concrete air entraining agent in the step (4) comprises the following components in parts by weight: 100-120 parts of pure water, 2.5-3.5 parts of sodium hydroxide, 4-6 parts of rosin-based cellulose ether, 1-2 parts of sodium tripolyphosphate aqueous solution with mass concentration of 2% -3%, and 5-15 parts of triethanolamine.
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Country or region after: China Address after: 843000 West Industrial Park Development Zone, Aksu City, Aksu Prefecture, Xinjiang Uygur Autonomous Region Applicant after: Xinjiang Hengtai Linmao Material Technology Co.,Ltd. Address before: 843000 West Industrial Park Development Zone, Aksu City, Aksu Prefecture, Xinjiang Uygur Autonomous Region Applicant before: Aksu Hengtai New Building Materials Co.,Ltd. Country or region before: China |