CN105732442A - Oligomer surfactant, and preparation method and application thereof - Google Patents

Oligomer surfactant, and preparation method and application thereof Download PDF

Info

Publication number
CN105732442A
CN105732442A CN201610055646.9A CN201610055646A CN105732442A CN 105732442 A CN105732442 A CN 105732442A CN 201610055646 A CN201610055646 A CN 201610055646A CN 105732442 A CN105732442 A CN 105732442A
Authority
CN
China
Prior art keywords
oligomeric
type surfactant
organic solvent
surfactant
react
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201610055646.9A
Other languages
Chinese (zh)
Other versions
CN105732442B (en
Inventor
陈健
乔敏
高南萧
冉千平
吴井志
吕志锋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BOT NEW MATERIALS TAIZHOU Co Ltd
Sobute New Materials Co Ltd
Original Assignee
BOT NEW MATERIALS TAIZHOU Co Ltd
Sobute New Materials Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BOT NEW MATERIALS TAIZHOU Co Ltd, Sobute New Materials Co Ltd filed Critical BOT NEW MATERIALS TAIZHOU Co Ltd
Priority to CN201610055646.9A priority Critical patent/CN105732442B/en
Publication of CN105732442A publication Critical patent/CN105732442A/en
Application granted granted Critical
Publication of CN105732442B publication Critical patent/CN105732442B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
    • 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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/16—Sulfur-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C309/07—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton
    • C07C309/09—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing etherified hydroxy groups bound to the carbon skeleton
    • C07C309/10—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing etherified hydroxy groups bound to the carbon skeleton with the oxygen atom of at least one of the etherified hydroxy groups further bound to an acyclic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides an oligomer surfactant, and a preparation method and application thereof. The oligomer surfactant has high surface activity, and excellent foaming and foam stabilizing properties. The oligomer surfactant has a specific structure: the molecule contains 3-7 hydrophobic chain segments and hydrophilic units, wherein each hydrophobic chain segment is a C8-C18 alkyl chain, and each hydrophilic unit is composed of 0-3 epoxy units and sulfate groups which are connected in the position near the hydrophilic unit through chemical bond covalence. The preparation method comprises the following steps: carrying out reaction on an alkyl epoxy compound B and a polylol A to generate an intermediate C, and sequentially modifying the hydrophilic epoxy units and sulfate groups on the intermediate C, thereby obtaining the oligomer surfactant. The oligomer surfactant has excellent air-entraining and foam stabilizing property when being used as a concrete air entraining agent; and meanwhile, the hardened concrete has excellent aerated structure and can not generate great impact on the setting strength of the concrete.

Description

Oligomeric-type surfactant, its preparation method and application
Technical field
The present invention relates to a kind of oligomeric-type surfactant, its preparation method and application, belong to concrete admixture field.
Background technology
In recent years, along with the development of high performance concrete, people are for concrete durability also pay attention to day by day, and the research and development of air entraining agent and production are increasingly becoming the focus in additive field.In concrete-agitating process, mix air entraining agent, it is possible to mix and stir newly and maturing introduces bubble small, uniform, airtight in right amount, thus improving concrete endurance quality and anti-thawing performance.Air entraining agent conventional at present includes rosin based air entraining agent, saponins air entraining agent, alkylsulfonate air entraining agent etc..Finding out from their chemical constitution, they are a kind of surfactants, and namely one end is hydrophobic segment, and the other end is the amphipathic single chain molecule of Hydrophilic ionic groups.This molecule can be aligned at gas-liquid interface by the heat resistance and salt tolerance between hydrophobic chain, thus reducing the surface tension of aqueous solution so that bubble is more prone to generate.But, between hydrophilic ionic group, the repulsive interaction of like charges hinders its close-packed arrays at gas-liquid interface so that surfactant molecule spacing increases.Which has limited their surface activity so that their bleed scarce capacity, or the bubble diameter introduced is big, size is uneven, elastic little, the poor stability of film, it is impossible to meet the concrete requirement of modern high performance.
Double type surfactant (GeminiSurfactants) is the novel surfactant that a class has special construction.Containing two hydrophilic ionic groups and two hydrophobic segments in its molecule, near hydrophilic group place, by bridge joint group by covalently bound two hydrophobic segments of chemical bond.Research shows, this structure makes the Coulomb repulsion between ionic group significantly be weakened because limiting by chemical bond, distance between hydrophobic segment furthers significantly simultaneously, enhance heat resistance and salt tolerance, enable the arrangement that surfactant molecule is tightr at gas-liquid interface, orderly, therefore there is higher surface activity (Angew.Chem.Int.Ed.2000,39,1906-1920).Patent documentation CN102641691A discloses a kind of anionic gemini surfactant, and compared to traditional strand type surfactant, it can more effectively reduce the surface tension of aqueous solution.Patent documentation CN104496525A discloses a kind of concrete air-entrainer containing double type surfactant, and compared to traditional concrete air-entrainer, it has more outstanding bleed and foam stability energy, concrete hardening strength will not be produced considerable influence simultaneously.
Oligomeric-type surfactant (OligomericSurfactants) is the further extension on double type surfactant basis, by the strand type surfactants of more than three covalently bound by chemical bond near hydrophilic group place.Researcher finds, compared to strand and double type surfactant, oligomeric-type surfactant has higher surface activity and better foams performance (Langmuir2012,28,9322-9331；CN103691360B；CN104263342A).At present to the research of oligomeric-type surfactant also in the starting stage, mainly there are trimerization type, four poly-type, hexapoly types etc.；Its practical application in engineering report is less, it is applied to concrete air-entrainer field and has no report especially.
Summary of the invention
Goal of the invention
It is an object of the present invention to provide a kind of oligomeric-type surfactant, there is high surface activity, and excellent foaming and foam stability energy.
The preparation method that it is a further object to provide described oligomeric-type surfactant.
It is a further object to provide the application of described oligomeric-type surfactant.
Summary of the invention
According to the first aspect of the invention, the invention provides a kind of oligomeric-type surfactant, its general structure is as follows:
Wherein R1=CH3(CH2)a, the integer of a=7～17；R2=(CH2CH2O)b, b=0,1,2 or 3；N=1,2,3,4 or 5；M=K or Na.
Containing 3～7 hydrophobic segments and hydrophilic unit in described oligomeric-type surfactant molecule, wherein hydrophobic segment is the alkyl chain (R containing 8～18 carbon1), hydrophilic unit is 0～3 epoxide unit (R2) and sulfuric acid group, covalently bound by chemical bond near hydrophilic unit place between them.This structure overcomes the electrostatic repulsion between sulfate radical, furthered the distance between hydrophobic segment simultaneously, enhance their heat resistance and salt tolerance, enable them in the more closely orderly arrangement of gas-liquid interface, therefore possesses traditional performance not available for single linked list surface-active agent, such as higher surface activity, better foaming and foam stability energy etc..
According to the second aspect of the invention, it is provided that the preparation method of described oligomeric-type surfactant, b=1,2 or when 3, synthetic route is as follows:
During b=0, synthetic route is as follows:
Said synthesis route adopts response type well known in the art to realize, and first passes through alkyl epoxy compound B and polyhydric alcohol A and reacts generation intermediate C, then modifies hydrophilic epoxide unit and sulfuric acid group on intermediate C in order.
Concrete, described preparation method comprises the following steps:
(1) polyhydric alcohol A is put in reactor; under protective atmosphere, highly basic effect; it is changed into the alkali metal alcoholates of polyhydric alcohol A; add alkyl epoxy compound B; it is warming up at 70～90 DEG C and reacts 6～8 hours; intermediate C is obtained after neutralization, purification; the mol ratio of the described hydroxyl in polyhydric alcohol A and alkyl epoxy compound B is 1:(0.95～1.05); the carbon number of common commercially available alkyl epoxy compound B is even number; now corresponding a is odd number, such as 7,9,11,13,15,17；
(2) intermediate C is dissolved in the first organic solvent; put in reactor; under protective atmosphere, highly basic effect; it is changed into the alkali metal alcoholates of intermediate C; add ethylene carbonate, be warming up at 60～70 DEG C and react 6～8 hours, after neutralization, purification, obtain intermediate D; the mol ratio of the hydroxyl in described intermediate C and ethylene carbonate is 1:(0～3), step (2) is optional step；
(3) intermediate C or intermediate D, carbamide, sulfamic acid are dissolved in the second organic solvent, put in reactor, react 2～4 hours at 90～110 DEG C；Add MOH, react 10～30 minutes；Purification obtains described surfactant, hydroxyl in described intermediate C or intermediate D, carbamide, sulfamic acid, MOH mol ratio be 1:(0.01～0.03): (0.95～1.05): (0.95～1.05).
In described step (1), (2) polyhydric alcohol A or intermediate C through the alkali metal alcoholates that highly basic role transformation is corresponding be known technology, wherein highly basic generally selects NaH, Na or K, it is clear that step (1), (2) can adopt identical or different highly basic.Highly basic consumption and reaction temperature and time are also known to those skilled in the art to be known, and general highly basic consumption is (0.95～1.05) times of polyhydric alcohol A or the intermediate C institute hydroxyl mole of effect, reacts 1～2 hour at 40～60 DEG C.
Described step (1), (2), (3) described neutralization, purification step can be required to be determined according to the application of concrete reaction system and end product by those skilled in the art.Preferably,
The neutralization of step (1), purification step be: the pH value of solution is adjusted to 6～7, extracts with dichloromethane subsequently, be dried with anhydrous sodium sulfate, through filtering and decompression distillation, obtains intermediate C；
The neutralization of step (2), purification step be: the pH value of solution is adjusted to 6～7, and decompression is distilled off the first organic solvent, extracts with dichloromethane subsequently, is dried with anhydrous sodium sulfate, through filtering and decompression distillation, obtains intermediate D；
The purification step of step (3) is: decompression is distilled off the second organic solvent, gained crude product washes of absolute alcohol, obtains described surfactant after sucking filtration, vacuum drying.
Involved organic solvent can be selected according to the physical property feature of reaction system by those skilled in the art.Preferably,
First organic solvent described in step (2) is oxolane, and it is 5%～50% that intermediate C is dissolved in the mass percent concentration after the first organic solvent；
Second organic solvent described in step (3) is DMF, and the gross mass percent concentration that intermediate C or intermediate D, carbamide, sulfamic acid are dissolved in the second organic solvent is 5%～50%.
As known technology, step (1), (2) described reaction should carry out under anaerobic, it is therefore desirable to provide protective atmosphere.It is generally selected nitrogen protection, there is cheap and easily-available advantage.
According to the third aspect of the invention we, the application as concrete air-entrainer of the described oligomeric-type surfactant is additionally provided.
Oligomeric-type surfactant of the present invention can reduce the surface tension of aqueous solution efficiently, there is good bleed and foam stabilizing effect, the molecule being primarily due to this structure can overcome electrostatic repulsion well, strengthen hydrophobic interaction simultaneously, it is enable closely to arrange at gas-liquid interface, more effectively reduce the surface tension of liquid, be also just more beneficial for the generation of small, uniform foam and stable.Described oligomeric-type surfactant not only has excellent bleed and foam stability energy when being used as concrete air-entrainer, maturing has preferably air hole structure simultaneously, and concrete hardening strength will not be produced considerable influence.
When surfactant of the present invention is used as concrete air-entrainer, after being dissolved in the water together with other additives, add in concrete and stir.The solid volume of suggestion folding is the ten thousand of Binder Materials quality/(0.2～2) in concrete.
Accompanying drawing explanation
Fig. 1: synthetic example 1 gained oligomeric-type surfactant A 7B0N1's1HNMR spectrogram；
Fig. 2: synthetic example 2 gained oligomeric-type surfactant A 9B0N1's1HNMR spectrogram；
Fig. 3: synthetic example 3 gained oligomeric-type surfactant A 11B1N2's1HNMR spectrogram；
Fig. 4: synthetic example 4 gained oligomeric-type surfactant A 13B1N3's1HNMR spectrogram；
Fig. 5: synthetic example 5 gained oligomeric-type surfactant A 15B2N4's1HNMR spectrogram；
Fig. 6: synthetic example 6 gained oligomeric-type surfactant A 17B3N5's1HNMR spectrogram；
Fig. 7: the surface tension of different surfaces activating agent and concentration relationship curve.
Detailed description of the invention
Material used by the present invention is all being purchased product, all reagent (analytical pure) that wherein oligomeric-type surfactant agent synthesis is used are all purchased from lark prestige Science and Technology Ltd., organic solvent (chemical pure) is all purchased from Chemical Reagent Co., Ltd., Sinopharm Group, and polycarboxylate water-reducer is from Jiangsu Subotexin Material Co., Ltd.
Synthetic example 1
10mmol glycerol is put in reactor, adds the sodium hydride of 30mmol under nitrogen protection, react 1 hour at 40 DEG C.Add the epoxy certain herbaceous plants with big flowers alkane of 30mmol, be warming up at 70 DEG C and react 6 hours.With dilute hydrochloric acid, the pH value of solution is adjusted to 6～7, extracts with 40mL dichloromethane subsequently, be dried with anhydrous sodium sulfate, through filtering and decompression distillation, obtain faint yellow solid, for intermediate C.
10mmol intermediate C, 0.3mmol carbamide, 30mmol sulfamic acid are dissolved in 40mLDMF, put in reactor, react 2 hours at 90 DEG C.Add 30mmol sodium hydroxide, react 10 minutes.Decompression is distilled off solvent, gained crude product washes of absolute alcohol, obtains faint yellow solid, for end product oligomeric-type surfactant (code name is A7B0N1, and nuclear magnetic spectrogram is as shown in Figure 1), R after sucking filtration, vacuum drying1=CH3(CH2)a, a=7；R2=(CH2CH2O)b, b=0；N=1；M=Na.
Synthetic example 2
10mmol glycerol is put in reactor, adds the sodium hydride of 30mmol under nitrogen protection, react 1 hour at 40 DEG C.Add the Epoxydodecane of 30mmol, be warming up at 70 DEG C and react 6 hours.With dilute hydrochloric acid, the pH value of solution is adjusted to 6～7, extracts with 40mL dichloromethane subsequently, be dried with anhydrous sodium sulfate, through filtering and decompression distillation, obtain faint yellow solid, for intermediate C.
10mmol intermediate C, 0.3mmol carbamide, 30mmol sulfamic acid are dissolved in 40mLDMF, put in reactor, react 2 hours at 90 DEG C.Add 30mmol sodium hydroxide, react 10 minutes.Decompression is distilled off solvent, gained crude product washes of absolute alcohol, obtains faint yellow solid, for end product oligomeric-type surfactant (code name is A9B0N1, and nuclear magnetic spectrogram is as shown in Figure 2), R after sucking filtration, vacuum drying1=CH3(CH2)a, a=9；R2=(CH2CH2O)b, b=0；N=1；M=Na.
Synthetic example 3
10mmol erythrol is put in reactor, adds the sodium of 40mmol under nitrogen protection, react 1.5 hours at 50 DEG C.Add the epoxy tetradecane of 40mmol, be warming up at 80 DEG C and react 7 hours.With dilute hydrochloric acid, the pH value of solution is adjusted to 6～7, extracts with 50mL dichloromethane subsequently, be dried with anhydrous sodium sulfate, through filtering and decompression distillation, obtain faint yellow solid, for intermediate C.
10mmol intermediate C is dissolved in 40mL oxolane, puts in reactor, add the sodium hydride of 40mmol under nitrogen protection, react 1 hour at 40 DEG C.Add the ethylene carbonate of 40mmol, be warming up at 60 DEG C and react 6 hours.With dilute hydrochloric acid, the pH value of solution being adjusted to 6～7, decompression is distilled off oxolane, extracts with 40mL dichloromethane subsequently, is dried with anhydrous sodium sulfate, through filtering and decompression distillation, obtains faint yellow solid, for intermediate D.
10mmol intermediate D, 0.8mmol carbamide, 40mmol sulfamic acid are dissolved in 50mLDMF, put in reactor, react 3 hours at 100 DEG C.Add 40mmol sodium hydroxide, react 20 minutes.Decompression is distilled off solvent, gained crude product washes of absolute alcohol, obtains faint yellow solid, for end product oligomeric-type surfactant (code name is A11B1N2, and nuclear magnetic spectrogram is as shown in Figure 3), R after sucking filtration, vacuum drying1=CH3(CH2)a, a=11；R2=(CH2CH2O)b, b=1；N=2；M=Na.
Synthetic example 4
10mmol pentite is put in reactor, adds the sodium of 50mmol under nitrogen protection, react 1.5 hours at 50 DEG C.Add the epoxyhexadecane of 50mmol, be warming up at 80 DEG C and react 7 hours.With dilute hydrochloric acid, the pH value of solution is adjusted to 6～7, extracts with 50mL dichloromethane subsequently, be dried with anhydrous sodium sulfate, through filtering and decompression distillation, obtain faint yellow solid, for intermediate C.
10mmol intermediate C is dissolved in 40mL oxolane, puts in reactor, add the sodium hydride of 50mmol under nitrogen protection, react 1 hour at 40 DEG C.Add the ethylene carbonate of 50mmol, be warming up at 60 DEG C and react 6 hours.With dilute hydrochloric acid, the pH value of solution being adjusted to 6～7, decompression is distilled off oxolane, extracts with 40mL dichloromethane subsequently, is dried with anhydrous sodium sulfate, through filtering and decompression distillation, obtains faint yellow solid, for intermediate D.
10mmol intermediate D, 1.0mmol carbamide, 50mmol sulfamic acid are dissolved in 50mLDMF, put in reactor, react 3 hours at 100 DEG C.Add 50mmol sodium hydroxide, react 20 minutes.Decompression is distilled off solvent, gained crude product washes of absolute alcohol, obtains faint yellow solid, for end product oligomeric-type surfactant (code name is A13B1N3, and nuclear magnetic spectrogram is as shown in Figure 4), R after sucking filtration, vacuum drying1=CH3(CH2)a, a=13；R2=(CH2CH2O)b, b=1；N=3；M=Na.
Synthetic example 5
10mmol hexanhexol is put in reactor, adds the potassium of 60mmol under nitrogen protection, react 2 hours at 60 DEG C.Add the epoxy octadecane of 60mmol, be warming up at 80 DEG C and react 8 hours.With dilute hydrochloric acid, the pH value of solution is adjusted to 6～7, extracts with 60mL dichloromethane subsequently, be dried with anhydrous sodium sulfate, through filtering and decompression distillation, obtain faint yellow solid, for intermediate C.
10mmol intermediate C is dissolved in 50mL oxolane, puts in reactor, add the sodium of 60mmol under nitrogen protection, react 1.5 hours at 50 DEG C.Add the ethylene carbonate of 120mmol, be warming up at 65 DEG C and react 7 hours.With dilute hydrochloric acid, the pH value of solution being adjusted to 6～7, decompression is distilled off oxolane, extracts with 50mL dichloromethane subsequently, is dried with anhydrous sodium sulfate, through filtering and decompression distillation, obtains faint yellow solid, for intermediate D.
10mmol intermediate D, 1.8mmol carbamide, 60mmol sulfamic acid are dissolved in 60mLDMF, put in reactor, react 4 hours at 110 DEG C.Add 60mmol sodium hydroxide, react 30 minutes.Decompression is distilled off solvent, gained crude product washes of absolute alcohol, obtains faint yellow solid, for end product oligomeric-type surfactant (code name is A15B2N4, and nuclear magnetic spectrogram is as shown in Figure 5), R after sucking filtration, vacuum drying1=CH3(CH2)a, a=15；R2=(CH2CH2O)b, b=2；N=4；M=Na.
Synthetic example 6
10mmol volemitol is put in reactor, adds the potassium of 70mmol under nitrogen protection, react 2 hours at 60 DEG C.Add the epoxy eicosane of 70mmol, be warming up at 70 DEG C and react 8 hours.With dilute hydrochloric acid, the pH value of solution is adjusted to 6～7, extracts with 60mL dichloromethane subsequently, be dried with anhydrous sodium sulfate, through filtering and decompression distillation, obtain faint yellow solid, for intermediate C.
10mmol intermediate C is dissolved in 60mL oxolane, puts in reactor, add the potassium of 70mmol under nitrogen protection, react 2 hours at 60 DEG C.Add the ethylene carbonate of 210mmol, be warming up at 70 DEG C and react 8 hours.With dilute hydrochloric acid, the pH value of solution being adjusted to 6～7, decompression is distilled off oxolane, extracts with 60mL dichloromethane subsequently, is dried with anhydrous sodium sulfate, through filtering and decompression distillation, obtains faint yellow solid, for intermediate D.
10mmol intermediate D, 2.1mmol carbamide, 70mmol sulfamic acid are dissolved in 60mLDMF, put in reactor, react 4 hours at 110 DEG C.Add 70mmol sodium hydroxide, react 30 minutes.Decompression is distilled off solvent, gained crude product washes of absolute alcohol, obtains faint yellow solid, for end product oligomeric-type surfactant (code name is A17B3N5, and nuclear magnetic spectrogram is as shown in Figure 6), R after sucking filtration, vacuum drying1=CH3(CH2)a, a=17；R2=(CH2CH2O)b, b=3；N=5；M=Na.
Synthesis comparative example 1
10mmol lauryl alcohol, 0.1mmol carbamide, 10mmol sulfamic acid are dissolved in 40mLDMF, put in reactor, react 2 hours at 90 DEG C.Add 10mmol sodium hydroxide, react 10 minutes.Decompression is distilled off solvent, gained crude product washes of absolute alcohol, sucking filtration, obtains white solid, for end product (code name is strand-1) after vacuum drying.
Synthesis comparative example 2
10mmol ethylene glycol is put in reactor, adds the sodium hydride of 20mmol under nitrogen protection, react 1 hour at 40 DEG C.Add the epoxy tetradecane of 20mmol, be warming up at 70 DEG C and react 6 hours.With dilute hydrochloric acid, the pH value of solution is adjusted to 6～7, extracts with 40mL dichloromethane subsequently, be dried with anhydrous sodium sulfate, through filtering and decompression distillation, obtain weak yellow liquid, for intermediate C.
10mmol intermediate C, 0.2mmol carbamide, 20mmol sulfamic acid are dissolved in 40mLDMF, put in reactor, react 2 hours at 90 DEG C.Add 20mmol sodium hydroxide, react 10 minutes.Decompression is distilled off solvent, gained crude product washes of absolute alcohol, sucking filtration, obtains faint yellow solid, for end product (code name is Shuangzi-1) after vacuum drying.
Application Example 1
By sample A7B0N1, A9B0N1, A11B1N2, A13B1N3, A15B2N4, A17B3N5 of synthetic example 1～6 preparation, and comparative example strand-1, Shuangzi-1 are made into the aqueous solution of variable concentrations, utilize surface tension instrument to measure the surface tension of solution.Fig. 7 is the graph of relation of aqueous solution surface tension and sample concentration, as can be seen from the figure, compared to the surfactant of strand and Shuangzi structure, faster, and the degree declined is also bigger for the speed that six kinds of oligomeric-type surfactants can make solution surface tension decline.Illustrate that they have the surface activity higher than strand and double type surfactant, be more favorable to the generation of bubble.
Application Example 2
Sample A7B0N1, A9B0N1, A11B1N2, A13B1N3, A15B2N4, A17B3N5 prepared by synthetic example 1～6, and comparative example strand-1, Shuangzi-1 are made into the aqueous solution that concentration is 1%, the Roche foam meter method utilizing GB/T13173-91 standard measures the foam height of solution, and measurement result is as shown in table 1.As can be seen from the table, compared to the surfactant of strand and Shuangzi structure, initial, 3 minutes, the 5 minutes foam heights of six kinds of oligomeric-type surfactants (are designated as h respectively0min、h3min、h5min) be intended to higher, and the ratio (h of foam height and initial foam height after 5 minutes5min/h0min) bigger.Illustrate that they have the foamability higher than strand and double type surfactant and foam stability energy.
The solution foaming properties of table 1 different surfaces activating agent compares
Application Example 3
With reference to standard GB/T 8076-2008 " concrete admixture " relevant regulations, carry out the mensuration of concrete strength and air content using synthetic example gained surfactant as concrete air-entrainer, use Bubble Parameters analyzer to determine bubble structure and the parameter of corresponding concrete test piece simultaneously.The water reducer adopted in the present invention is polycarboxylate water-reducer, and the solid volume of folding is 0.15%；Cement is little wild field 52.5R.P.II cement；Sand is modulus of fineness is the medium sand of Mx=2.6；Stone is particle diameter is the rubble of 5-25mm continuous grading.Concrete mix used is: cement 330kg, sand 729kg, great Shi 714kg, gravelstone 476kg, water 1.25kg.
For different samples, we have employed the solid volume of different foldings, it is therefore an objective in order to obtain close initial air content, in order to the comparison of follow-up performance.Experimental result is as shown in table 2.As can be seen from the table, when initial air content is substantially the same, contrast strand and double type surfactant, and commercially available colophonium pyrolytic polymer air entraining agent, the oligomeric-type surfactant air content loss that the present invention develops is less, mean air bubble diameter and bubble gap factor are also less, and this illustrates that the present invention has better bleed and foam stability energy.Being found by strong concrete degrees of data, the different larval instar intensity of the test block of the oligomeric-type surfactant that the present invention develops will apparently higher than the intensity of test block of other three kinds of comparative sample.This illustrates that the oligomeric-type surfactant of the present invention is while possessing good bleed and foam stability energy, and the impact of concrete strength is less.
The concrete performance of the different air entraining agent of table 2 compares

Claims (7)

1. an oligomeric-type surfactant, its general structure is as follows:
Wherein R1=CH3(CH2)a, the integer of a=7～17；R2=(CH2CH2O)b, b=0,1,2 or 3；N=1,2,3,4 or 5；M=K or Na.
2. oligomeric-type surfactant as claimed in claim 1, it is characterised in that M=Na.
3. the preparation method of the oligomeric-type surfactant described in claim 1 or 2, it is characterised in that b=1,2 or when 3, synthetic route is as follows:
During b=0, synthetic route is as follows:
4. the preparation method of oligomeric-type surfactant as claimed in claim 3, it is characterised in that comprise the following steps:
(1) polyhydric alcohol A is put in reactor; under protective atmosphere, highly basic effect; it is changed into the alkali metal alcoholates of polyhydric alcohol A; add alkyl epoxy compound B; it is warming up at 70～90 DEG C and reacts 6～8 hours; the mol ratio obtaining intermediate C, the described hydroxyl in polyhydric alcohol A and alkyl epoxy compound B after neutralization, purification is 1:(0.95～1.05)；
(2) intermediate C is dissolved in the first organic solvent; put in reactor; under protective atmosphere, highly basic effect; it is changed into the alkali metal alcoholates of intermediate C; add ethylene carbonate, be warming up at 60～70 DEG C and react 6～8 hours, after neutralization, purification, obtain intermediate D; the mol ratio of the hydroxyl in described intermediate C and ethylene carbonate is 1:(0～3), step (2) is optional step；
(3) intermediate C or intermediate D, carbamide, sulfamic acid are dissolved in the second organic solvent, put in reactor, react 2～4 hours at 90～110 DEG C；Add MOH, react 10～30 minutes；Purification obtains described surfactant, hydroxyl in described intermediate C or intermediate D, carbamide, sulfamic acid, MOH mol ratio be 1:(0.01～0.03): (0.95～1.05): (0.95～1.05).
5. the preparation method of oligomeric-type surfactant as claimed in claim 4, it is characterised in that
The neutralization of step (1), purification step be: the pH value of solution is adjusted to 6～7, extracts with dichloromethane subsequently, be dried with anhydrous sodium sulfate, through filtering and decompression distillation, obtains intermediate C；
The neutralization of step (2), purification step be: the pH value of solution is adjusted to 6～7, and decompression is distilled off the first organic solvent, extracts with dichloromethane subsequently, is dried with anhydrous sodium sulfate, through filtering and decompression distillation, obtains intermediate D；
The purification step of step (3) is: decompression is distilled off the second organic solvent, gained crude product washes of absolute alcohol, sucking filtration, obtains described surfactant after vacuum drying.
6. the preparation method of oligomeric-type surfactant as claimed in claim 4, it is characterised in that
First organic solvent described in step (2) is oxolane, and it is 5%～50% that intermediate C is dissolved in the mass percent concentration after the first organic solvent；
Second organic solvent described in step (3) is DMF, and the gross mass percent concentration that intermediate C or intermediate D, carbamide, sulfamic acid are dissolved in the second organic solvent is 5%～50%.
7. the oligomeric-type surfactant described in claim 1 or 2 is as the application of concrete air-entrainer.
CN201610055646.9A 2016-01-27 2016-01-27 Oligomeric-type surfactant, its preparation method and application Active CN105732442B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610055646.9A CN105732442B (en) 2016-01-27 2016-01-27 Oligomeric-type surfactant, its preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610055646.9A CN105732442B (en) 2016-01-27 2016-01-27 Oligomeric-type surfactant, its preparation method and application

Publications (2)

Publication Number Publication Date
CN105732442A true CN105732442A (en) 2016-07-06
CN105732442B CN105732442B (en) 2017-11-03

Family

ID=56246655

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610055646.9A Active CN105732442B (en) 2016-01-27 2016-01-27 Oligomeric-type surfactant, its preparation method and application

Country Status (1)

Country Link
CN (1) CN105732442B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106977428A (en) * 2017-03-17 2017-07-25 内蒙古工业大学 Improve the method for preparing lauryl sodium sulfate
CN108250204A (en) * 2016-12-28 2018-07-06 江苏苏博特新材料股份有限公司 Gemini surfactant and its preparation method and application
CN113121351A (en) * 2019-12-30 2021-07-16 江苏苏博特新材料股份有限公司 Efficient concrete foam stabilizer and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2181152B (en) * 1985-09-25 1989-09-20 Kao Corp Liquid detergent composition
US20060135391A1 (en) * 2004-12-17 2006-06-22 Scheibel Jeffrey J Modified alkoxylated polyol compounds
CN1843605A (en) * 2006-03-21 2006-10-11 华东理工大学 Anionic oligo surfactant and its preparation method
CN1894305A (en) * 2003-12-19 2007-01-10 宝洁公司 Modified alkoxylated polyol compounds
CN104447424A (en) * 2014-11-13 2015-03-25 武汉钢铁(集团)公司 Ammonium sulfamate demulsifier, synthesis method thereof and application of ammonium sulfamate in cold rolling of waste emulsion

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2181152B (en) * 1985-09-25 1989-09-20 Kao Corp Liquid detergent composition
CN1894305A (en) * 2003-12-19 2007-01-10 宝洁公司 Modified alkoxylated polyol compounds
US20060135391A1 (en) * 2004-12-17 2006-06-22 Scheibel Jeffrey J Modified alkoxylated polyol compounds
CN1843605A (en) * 2006-03-21 2006-10-11 华东理工大学 Anionic oligo surfactant and its preparation method
CN104447424A (en) * 2014-11-13 2015-03-25 武汉钢铁(集团)公司 Ammonium sulfamate demulsifier, synthesis method thereof and application of ammonium sulfamate in cold rolling of waste emulsion

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
韩恒等: "三联阴离子表面活性剂的合成及其表面化学性能", 《日用化学工业》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108250204A (en) * 2016-12-28 2018-07-06 江苏苏博特新材料股份有限公司 Gemini surfactant and its preparation method and application
CN108250204B (en) * 2016-12-28 2019-06-28 江苏苏博特新材料股份有限公司 Gemini surfactant and its preparation method and application
CN106977428A (en) * 2017-03-17 2017-07-25 内蒙古工业大学 Improve the method for preparing lauryl sodium sulfate
CN113121351A (en) * 2019-12-30 2021-07-16 江苏苏博特新材料股份有限公司 Efficient concrete foam stabilizer and preparation method thereof
CN113121351B (en) * 2019-12-30 2022-07-12 江苏苏博特新材料股份有限公司 Efficient concrete foam stabilizer and preparation method thereof

Also Published As

Publication number Publication date
CN105732442B (en) 2017-11-03

Similar Documents

Publication Publication Date Title
CN105732442A (en) Oligomer surfactant, and preparation method and application thereof
CN104140454A (en) Polyether amine based alkyl glycoside for drilling fluid and preparation method thereof
CN104774293A (en) Mud-resistant polycarboxylic acid water reducer and preparation method thereof
CN100465123C (en) Method of preparing poly carboxylic acid series water reducer using maleic anhydride
CN104628293A (en) Early strength type polycarboxylic acid water reducing agent, preparation method and use method thereof
CN108277012A (en) A kind of soil-solidified-agent and its application
CN107973536A (en) A kind of oligomeric-type concrete defoamer, its preparation method and application
CN105964185A (en) Asymmetric cationic Gemini surfactant containing hydroxyl group in coupling link
CN102558410B (en) Preparation method of self-assembled three-dimensional ordered polystyrene colloidal crystal
CN106220097A (en) A kind of concurrent factory formula reducing energy consumption and electric pole preparation method
CN104190314A (en) Fatty amine polyoxyethylene ether diethyl disulfonate surfactant and preparation method thereof
CN106188108A (en) The metal-organic framework materials of a kind of Cd and preparation method and applications
CN105727827B (en) Surfactant, its preparation method and application
CN101544682B (en) 11-keto-16,17-epoxyprogesterone and industrial production method
CN111377834A (en) Continuous preparation method of acetoacetamidosulfonic acid triethylamine
CN111073622B (en) Surfactant composition for improving recovery ratio and preparation method and application thereof
CN106566509B (en) A kind of ternary composite driving composition and its application in high temperature and high salt oil deposit
CN108250204B (en) Gemini surfactant and its preparation method and application
Wang et al. Synthesis and surface activity of biomass cardanol sulfonate surfactant
CN105645818A (en) Method for synthesizing modified aminosulfonate superplasticizer from wastewater produced in gamma acid production process
CN106566510B (en) A kind of ternary composite driving composition and its application in chemical flooding
CN113500188B (en) Three-dimensional metal fiber-cement-based composite material suitable for 3D printing and preparation method thereof
CN109679034A (en) A kind of high-adaptability ester group modified polycarboxylic acid water-reducing agent and its preparation and application
CN105949438B (en) Three kinds of biological base epoxies based on furan ring structure and its preparation method and application
CN101215117A (en) Low gas content polycarboxylic acids water reducing agent and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant