CN103012541B - Midbody of structure modified type tea-oil saponin and preparation method and application thereof - Google Patents
Midbody of structure modified type tea-oil saponin and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a midbody of a structure modified type tea-oil saponin. The midbody can be used for preparing the structure modified type tea-oil saponin, and the midbody self can be also used as a concrete air entraining agent in buildings and engineering.
Description
One, technical field
The present invention relates to a kind of intermediate of novel structural modification type cameclia oleifera saponin, this intermediate can be used for preparing structural modification type cameclia oleifera saponin, and himself also can directly be used as air entrapment agent.
Two, background technology
Admixture trace in concrete (ten thousand of cement consumption/several) air entrapment agent is one of effective measure that improve concrete durability, particularly frost resistance and deicer-scaling resistance.In the U.S., Canada, Japan and the developed country such as European, because they attach great importance to the weather resistance of engineering, air entrapment agent is the most frequently used admixture, and the concrete of mixing air entrapment agent accounts for 70-80% of concrete total amount, even more.
In China, except the related standards regulation of hydro-structure, outside the necessary admixture bleed extremely of concrete, Other Engineering is as highway, road, bridge, building, underground structure, the Important Project such as airfield runway all do not specify to mix air entrapment agent, therefore, in fact, except water conservancy project and northern harbour engineering, other Important Project are rarely mixed air entrapment agent.
Most of air entrapment agents are petrochemical compleies, paper pulp processed, papermaking and some other industrial byproduct.The modal chemical composition of air entrapment agent has five classes at present: 1. the sodium salt compound of rosin tree lipid; 2. soap compounds; 3. sulfonation hydrocarbon polymer; 4. alkyl-phenmethyl Sulfonates compound; 5. triterpenoid saponin natural product.
The air entrapment agent that China is early used is taking the rosined soap introduced from USSR (Union of Soviet Socialist Republics) as representative, the shortcoming of this air entrapment agent is in hot water, to dissolve, and causes strength decreased larger owing to introducing bubble, has therefore affected the air entrapment agent application in concrete works at home.Developed afterwards colophonium pyrolytic polymer and with washing composition, pulling open the surfactants such as powder is basic air entrapment agent, solubility has been improved greatly, but strength decreased is still larger.Until the early 1990s, domestic traditional commodities air entrapment agent majority is rosined soap type, also there is minority colophonium pyrolytic polymer type product, but also all there is unstable properties, poorly soluble, poor with other composition of concrete admixtures shortcoming, particularly with high-performance water reducing agent of new generation---the composite effect of poly carboxylic acid series water reducer is poorer, concrete strength is reduced to the shortcomings such as larger, restricted applying of air entrapment agent.
The VINSOL colophonium pyrolytic polymer air entrapment agent that the U.S. produces, performance quality is better, but price is more expensive.In general, the loss of strength rate that the air content of the every introducing 1% of existing air entrapment agent causes is about 4～7%, is generally 5%.
Three, summary of the invention
The object of the invention is to propose a kind of stable performance, solvability is good, with high-performance water reducing agent of new generation---poly carboxylic acid series water reducer composite effect is good, concrete strength is reduced to little air entrapment agent and preparation technology thereof, to improve concrete quality, particularly improve concrete weather resistance, frost resistance and deicer-scaling resistance.
For realizing the object of the invention, the present invention adopts following technical scheme:
It is a kind of suc as formula the structural modification type cameclia oleifera saponin shown in (I),
Further, the structural modification type cameclia oleifera saponin that can be used as air entrapment agent of the present invention, can directly make as follows:
(1) get hydrolysing oil TS 100 mass parts shown in formula IV, triphenylmethyl chloride 1～5 mass parts, bromination 1-p-methylphenyl-2-diethyl hexadecyldimethyl benzyl ammonium-1-acetone 1～3 mass parts, 10～20% formic acid 1～6 mass parts, at 160～200 DEG C of temperature stirring reaction 2～3 hours, obtain the compd A shown in product formula II after cooling;
(2) sucrose of 5～10 mass parts is dissolved in the water of 100 parts, add the trimethyl orthoacetate of 2～5 mass parts, stirring reaction 1～2 hour at 150～180 DEG C of temperature, then add 2～5% dilute hydrochloric acid 1～3 mass parts, stirring reaction adds caustic soda or soda ash 1～4 mass parts of 2-6% again after 1～3 hour, stir about 1～3 hour, finally add bromination 1-p-methylphenyl-2-diethyl hexadecyldimethyl benzyl ammonium-1-acetone 1～3 mass parts, 5～10% sodium methylate aqueous solution 4～5 mass parts, continue to stir 2～3 hours, obtain the compd B shown in product formula III;
(3) get the product compd A of 3～5 mass parts step (2) gained and the product compd B of 2～3 mass parts step (3) gained, mix, adding mass parts is the methylene diethyl ether of 0.5～1 part, stirring reaction 4～5 hours at 180～250 DEG C of temperature, be filled with hydrogen reducing again, remove unnecessary hydrogen, obtaining reduzate is the structural modification type cameclia oleifera saponin shown in formula (I).
Hydrolysing oil TS shown in formula IV also can be made air entrapment agent and use, but the air entrapment agent that the present invention proposes, main component is structural modification type cameclia oleifera saponin, structural modification type cameclia oleifera saponin of the present invention refines and obtains from tea seed grouts, on sasanguasaponin air entrapment agent basis, to its active ingredient---the chemical structure of sasanguasaponin is carried out molecular modification, and according to the synthesis technique feature of poly carboxylic acid series water reducer, further optimize operational path and the technical parameter of sasanguasaponin structural modification, through a series of reaction process, obtain the lower novel surfactant structure of surface tension of two hydrophilic, by adding suds-stabilizing agent A(propyl carbinol) and B(dimethyl dodecyl amine oxide), final acquisition foaming properties is excellent, with the effective air entrapment agent product innovation of other composition of concrete admixture.
The present invention recommends tea seed grouts directly to extract sasanguasaponin composition and makes structural modification type cameclia oleifera saponin of the present invention, the present invention utilizes the characteristic that is rich in sasanguasaponin in tea seed grouts, from plant material, extract, then through hydrolysis and a series of molecular structure alteration and other comprehensive technical measure, obtain the hydrophilic midparent oil type in two, new air entraining product that foaming properties is good.The present invention recommends following method to prepare the hydrolysing oil TS shown in formula IV: get the tea seed grouts particle that grain diameter is less than 2.5mm, taking mass concentration as 50%～80% alcoholic solvent, normal temperature dipping 1～3 hour, described alcoholic solvent was methyl alcohol or ethanol; The amount of added alcoholic solvent is as the criterion below so that tea seed grouts particle is all immersed to alcoholic solvent liquid level, filter to obtain tea seed grouts extracting solution, filter residue at 50～100 DEG C precipitation in have alcohol mass content emit lower than 1% time and discard, the object of filter residue precipitation mainly considers that the alcohol of recovery can recycle, and the filter residue simultaneously discarding is compared with environmental protection and can be used as the utilizations such as fuel; Described tea seed grouts extracting solution is concentrated under 50～100 DEG C of conditions, when being concentrated into solid content in enriched material and being 30～50%, take out enriched material and be sasanguasaponin, adding quality is 5～15% caustic soda or soda ash of enriched material quality, described caustic soda or soda ash add after with a small amount of water dissolution, under 100～120 DEG C of temperature condition, stir 30～60 minutes, obtaining extract is the hydrolysing oil TS shown in formula IV again; While adding caustic soda or soda ash, add after conventionally first dissolving caustic soda or soda ash with the water that is enough to dissolve caustic soda or soda ash, the implication of " on a small quantity " refers to that the water yield that can allow caustic soda or soda ash dissolve is just enough here, and this water yield can not allow other impact of reaction generation.
The intermediate of the structural modification type cameclia oleifera saponin described in the present invention also provides, compd B shown in the compd A as shown in formula II and formula III.Compd A as shown in formula II provided by the present invention is also a kind of sasanguasaponin of modification, also can be used as concrete air entrapment agent and uses, and the embodiment of the present invention 9 has exemplified the performance that compd A uses as air entrapment agent.
The preparation method of structural modification type cameclia oleifera saponin of the present invention, carry out as follows: get the compd A of 3～5 mass parts and the compd B of 2～3 mass parts, mix, add the methylene diethyl ether of 0.5～1 mass parts, stirring reaction 4～5 hours at 180～250 DEG C of temperature, be filled with hydrogen reducing again, remove unnecessary hydrogen, obtaining reduzate is the structural modification type cameclia oleifera saponin shown in formula (I);
Described compd A makes as follows: get hydrolysing oil TS 100 mass parts shown in formula IV, triphenylmethyl chloride 1～5 mass parts, bromination 1-p-methylphenyl-2-diethyl hexadecyldimethyl benzyl ammonium-1-acetone 1～3 mass parts, 10～20% formic acid 1～6 mass parts, at 160～200 DEG C of temperature stirring reaction 2～3 hours, obtain the compd A shown in formula II after cooling;
Described compd B makes as follows: the sucrose of 5～10 mass parts is dissolved in the water of 100 parts, add the trimethyl orthoacetate of 2～5 mass parts, stirring reaction 1～2 hour at 150～180 DEG C of temperature, then add 2～5% dilute hydrochloric acid 1～3 mass parts, stirring reaction adds 2～6% caustic soda or soda ash 1～4 mass parts stir about 1～3 hour again after 1～3 hour, finally add bromination 1-p-methylphenyl-2-diethyl hexadecyldimethyl benzyl ammonium-1-acetone 1～3 mass parts, 5～10% sodium methylate aqueous solution 4～5 mass parts, continue to stir 2～3 hours, products therefrom is the compd B shown in formula III.Described compd B is the intermediate of using for grafting addition.
Structural modification type cameclia oleifera saponin of the present invention can be used as architecture/engineering concrete air-entrainer.Structural modification type cameclia oleifera saponin of the present invention can be directly uses as concrete air-entrainer, also can add to be re-used as air entrapment agent after suds-stabilizing agent and to use.
When structural modification type cameclia oleifera saponin of the present invention directly uses as air entrapment agent, using method is as follows: in the time of concrete batching, in concrete, add the structural modification type cameclia oleifera saponin of cement quality 0.02～0.12% in concrete foundation formula, quality is the water reducer of cement quality 1～2% in concrete foundation formula, described water reducer is polycarboxylate high performance water-reducing agent or naphthalene water reducer, churning time is controlled at 2～4 minutes, then carries out other operation prepared by concrete.Binary or multiple copolymer that polycarboxylate high performance water-reducing agent of the present invention is polymerized by grafted monomer such as vinylformic acid, maleic anhydride, methacrylic acid, Hydroxyethyl acrylates conventionally, can be from commercially available.Naphthalene water reducer also can derive from commercially available.
Structural modification type cameclia oleifera saponin of the present invention adds when being re-used as air entrapment agent after suds-stabilizing agent and using, application method is: get described structural modification type cameclia oleifera saponin, add suds-stabilizing agent A (propyl carbinol) and suds-stabilizing agent B (dimethyl dodecyl amine oxide) to stir 1～2 hour, control temperature to 60-80 DEG C, drip and add water to solid content and reach 20-25%, stir and make air entrapment agent, described structural modification type cameclia oleifera saponin, suds-stabilizing agent A, suds-stabilizing agent B mass ratio are 100:1～3:1～2; Described application method is: in the time of concrete batching, described air entrapment agent, the quality that adds cement quality 0.02～0.12% in concrete foundation formula in concrete is the polycarboxylate high performance water-reducing agent of cement quality 1～2% in concrete foundation formula, churning time is controlled at 2～4 minutes, then carries out other agitating procedure prepared by concrete.Equally, the polycarboxylate high performance water-reducing agent here also can substitute with naphthalene water reducer, as naphthene sulfonic acid-formaldehyde condensation products.
Suds-stabilizing agent A of the present invention is propyl carbinol, and suds-stabilizing agent B is dimethyl dodecyl amine oxide.The said polycarboxylate high performance water-reducing agent of the present invention is binary or the multiple copolymer being polymerized by grafted monomer such as vinylformic acid, maleic anhydride, methacrylic acid, Hydroxyethyl acrylates, specifically has two types, ester type and ether type.
While using product of the present invention as air entrapment agent, recommend the mass ratio of cement, water, fine sand, rubble in described concrete foundation formula to be: 350:140-160:550-580:1200-1300(kg/m3)., preferably cement: tap water: medium sand: rubble=350:144:567:1256(kg/m3).
The invention still further relates to the building concrete air entrapment agent that contains structural modification type cameclia oleifera saponin, described air entrapment agent makes as follows:
(a) get the tea seed grouts particle that grain diameter is less than 2.5mm, taking mass concentration as 50%～80% alcoholic solvent, normal temperature dipping 1～3 hour, described alcoholic solvent was methyl alcohol or ethanol; Filter to obtain tea seed grouts extracting solution, filter residue at 50～100 DEG C precipitation in have alcohol mass content emit lower than 1% time, tea seed grouts extracting solution is concentrated under 50～100 DEG C of conditions, be concentrated into solid the containing while being 30～50% in enriched material, take out enriched material and be sasanguasaponin, adding quality is 5～15% caustic soda or soda ash of enriched material quality, described caustic soda or soda ash add after with a small amount of water dissolution, under 100～120 DEG C of temperature condition, stir 30～60 minutes, obtaining extract is the hydrolysing oil TS shown in formula IV again;
(b) get extract obtained 100 mass parts of step (a), the formic acid 1-6 mass parts of triphenylmethyl chloride 1～5 mass parts, bromination 1-p-methylphenyl-2-diethyl hexadecyldimethyl benzyl ammonium-1-acetone 1-3 mass parts, 10-20%, at 160～200 DEG C of temperature stirring reaction 2～3 hours, obtain the compd A shown in formula II after cooling;
(c) sucrose of 5～10 mass parts is dissolved in the water of 100 parts, add the trimethyl orthoacetate of 2～5 mass parts, stirring reaction 1～2 hour at 150～180 DEG C of temperature, then add 2～5% dilute hydrochloric acid 1～3 mass parts, stirring reaction adds the caustic soda of 2-6% or soda ash 1～4 mass parts stir about 1～3 hour again after 1～3 hour, finally add bromination 1-p-methylphenyl-2-diethyl hexadecyldimethyl benzyl ammonium-1-acetone 1～3 mass parts, 5～10% sodium methylate aqueous solution 4～5 mass parts, continue to stir 2～3 hours, obtain the compd B shown in formula III;
(d) get the product compd A of 3～5 mass parts step (b) gained and the product compd B of 2～3 mass parts step (c) gained, mix, adding mass parts is the methylene diethyl ether of 0.5～1 part, stirring reaction 4～5 hours at 180～250 DEG C of temperature, be filled with hydrogen reducing again, remove unnecessary hydrogen, obtaining reduzate is the structural modification type cameclia oleifera saponin shown in formula (I).
(e) get the reduzate that step (d) obtains, adding mass parts is suds-stabilizing agent A and the suds-stabilizing agent B stirring 1-2 hour of reduzate 1～3%, while cooling to 60-80 DEG C, drip water, while reaching 20-25% Deng solid content, make described air entrapment agent, described suds-stabilizing agent A is propyl carbinol, described suds-stabilizing agent B is dimethyl dodecyl amine oxide, and reduzate, suds-stabilizing agent A, suds-stabilizing agent B mass ratio that described step (d) obtains are 100:1～3:1～2.
The structural modification type cameclia oleifera saponin that the present invention proposes is as follows as the principle of building concrete air entrapment agent: normally a kind of tensio-active agent of air entrapment agent, there is the organic compound of long chain molecule structure, and hydrophilic radical is contained in its one end; The other end contains hydrophobic group.Although triterpenoid saponin air entrapment agent foam exquisiteness is found in a large amount of research, but amount of air entrainment is less, use cost is higher, also falls into debt, in order to overcome above shortcoming with the composite effect of poly carboxylic acid series water reducer simultaneously, contriver carries out molecular modification to its active ingredient structure, make its final structure be modified into two hydrophilic, the new texture of middle oleophylic, it is mainly by monosaccharide groups, glucoside key and glucoside unit base, the compositions such as polysaccharide-based.In monose and polysaccharide, having a lot of hydroxyls (OH) to form hydrogen bond with water molecules, thereby have very strong wetting ability, is a hydrophilic radical; And glucoside unit in glucoside unit base has lipophilicity, it is hydrophobic group.Therefore structural modification type cameclia oleifera saponin is not only containing hydrophilic radical but also containing the amphipathic molecule of the group of surging.After structural modification type cameclia oleifera saponin is water-soluble, molecule just aligns at gas---and on liquid interface, reduce the surface tension of solution, thereby made the generation of new interface or bubble become easier.
Compared with prior art, the invention has the beneficial effects as follows: a kind of new structural modification type cameclia oleifera saponin is provided, this structural modification type cameclia oleifera saponin can be made concrete air-entrainer, the present invention also provides structural modification type cameclia oleifera saponin specifically as the application of concrete air-entrainer, and provide the building concrete that contains structural modification type cameclia oleifera saponin air entrapment agent, use air entrapment agent of the present invention, prepare advantage and effect that concrete has as follows:
(1) structural modification type cameclia oleifera saponin provided by the invention and to apply the production technique of its air entrapment agent of preparing reasonable, product has suitability widely in concrete works.
(2) concrete water-reducing ratio that prepared by air entrapment agent provided by the invention is greater than 6%; Reach 8%
(3) the concrete water bleeding rate that prepared by air entrapment agent provided by the invention drops to 8.6% by original 24.5%;
(4) the concrete concrete crushing strength rate of loss that prepared by air entrapment agent provided by the invention, the ultimate compression strength loss that per unit air content causes is less than 2%;
(5) concrete that prepared by air entrapment agent provided by the invention, in the time that air content is not more than 6%, concrete flexural strength can improve 10-30%;
(6) concrete that prepared by air entrapment agent provided by the invention, frost resistance improves more than 8 times;
(7) the agent on crack resistance of concrete deicer-scaling that prepared by air entrapment agent provided by the invention improves more than 5 times;
(8) other weather resistance of concrete that prepared by air entrapment agent provided by the invention as salt crystallization crush bad, alkali destruction etc. also obviously improve;
Structural modification type cameclia oleifera saponin provided by the present invention is as air entrapment agent, water-soluble and good with the plyability of other admixture, especially good with poly carboxylic acid series water reducer composite effect, overcome the precipitation that other air entrapment agent and poly carboxylic acid series water reducer compound tense occur, separate out phenomenon.
Four, embodiment
With specific embodiment, technical scheme of the present invention is described below, but protection scope of the present invention is not limited to this:
Embodiment 1
The first step: in the multi-function extractor of 3000L, add 500 kilograms to be tea seed grouts and 1500 kilograms of methyl alcohol that content is 70% of 2.5mm sieve through aperture, dipping extraction at normal temperatures 2 hours, after feed liquid separates with press filtration after filtration, filter residue in extractor carries out precipitation and recovery by hot steam, the filtrate having entered in 2000L concentration tank concentrates 3～4 hours the temperature of 80 DEG C, solid content in solution to be concentrated reaches 40%(concentrated solution quality and is about 150 kilograms) time, concentrate pump is delivered in the reactor of 2000L with pressure pump, first dissolve 1.5 kilograms of industrial caustic soda with 30 liters of pure water, again the caustic soda of dissolving is also added in reactor, at 110 DEG C of temperature, stir 50 minutes, obtaining product is the hydrolysing oil TS shown in formula IV.
Second step: in the reactor of the first step, add 4.5 kilograms of triphenylmethyl chlorides, 3 kilograms of bromination 1-p-methylphenyl-2-diethyl hexadecyldimethyl benzyl ammonium-1-acetone, 6 kilogram 15% formic acid, at 180 DEG C of temperature, stir 2 hours, obtaining product is compd A, cooling rear for subsequent use.
The 3rd step: add 500 kilograms of tap water and 40 kilograms of sucrose in the reactor of 1000L, sucrose is after stirring dissolving completely, add 15 kilograms of trimethyl orthoacetates, and stir 1.5 hours at 160 DEG C of temperature, then add the dilute hydrochloric acid of 10 kilogram 3%, continuing to stir after 2 hours adds the caustic soda of 15 kilogram 3% to stir 1 hour again, finally add the sodium methylate aqueous solution that 10 kilograms of bromination 1-p-methylphenyl-2-diethyl hexadecyldimethyl benzyl ammonium-1-acetone and 20 kilograms of concentration are 8% to continue to stir 2 hours, obtaining product is compd B, cooling rear for subsequent use.
The 4th step: get double centner second step gains and 50 kilogram of the 3rd step gains mixes in the reactor of 500L, add 20 kilograms of methylene diethyl ethers, at 200 DEG C of temperature, stir 5 hours, be filled with again 10L hydrogen in mixture, after 1 hour, remove unnecessary hydrogen, obtain the structural modification type cameclia oleifera saponin shown in formula (I), referred to as structural modification type cameclia oleifera saponin concrete air-entrainer (1).
Embodiment 2:
The first step: in the multi-function extractor of 3000L, add 500 kilograms to be tea seed grouts and 1500 kilograms of methyl alcohol that content is 70% of 2.5mm sieve through aperture, extract at normal temperatures 2 hours, after feed liquid separates with press filtration after filtration, filter residue in extractor carries out precipitation and recovery by hot steam, the filtrate having entered in 2000L concentration tank concentrates 3～4 hours the temperature of 80 DEG C, solid content in solution to be concentrated reaches 40%(concentrated solution quality and is about 150 kilograms) time, concentrate pump is delivered in the reactor of 2000L with pressure pump, first dissolve 1.5 kilograms of industrial soda ash with 30 liters of pure water, again the soda ash of dissolving is added in reactor, stir 50 minutes at 110 DEG C of temperature after, add 4.5 kilograms of triphenylmethyl chlorides, 3 kilograms of bromination 1-p-methylphenyl-2-diethyl hexadecyldimethyl benzyl ammonium-1-acetone, the formic acid of 6 kilogram 15%, at 180 DEG C of temperature, stir 2 hours, obtaining product is compd A, cooling rear for subsequent use.
Second step: add 500 kilograms of tap water and 40 kilograms of sucrose in the reactor of 1000L, sucrose is after stirring dissolving completely, add 15 kilograms of trimethyl orthoacetates, and stir 1.5 hours at 160 DEG C of temperature, then add the dilute hydrochloric acid of 10 kilogram 3%, continuing to stir after 2 hours adds the soda ash of 8 kilogram 3% to stir 1 hour again, finally add the sodium methylate aqueous solution that 10 kilograms of bromination 1-p-methylphenyl-2-diethyl hexadecyldimethyl benzyl ammonium-1-acetone and 20 kilograms of concentration are 8% to continue to stir 2 hours, obtaining product is compd B, cooling rear for subsequent use.
The 3rd step: get double centner the first step gains and 50 kilograms of second step gains mix in the reactor of 500L, add 20 kilograms of methylene diethyl ethers, at 200 DEG C of temperature, stir 5 hours, be filled with again 10L hydrogen in mixture, after 1 hour, remove unnecessary hydrogen, obtain the structural modification type cameclia oleifera saponin shown in formula (I); Continue to add again 2 kilograms of propyl carbinols and 1.5 kilograms of dimethyl dodecyl amine oxides to stir 1 hour, while cooling to 60 DEG C, drip tap water, while waiting solid content to reach 25%, can make the concrete air-entrainer containing structural modification type cameclia oleifera saponin.Referred to as structural modification type cameclia oleifera saponin concrete air-entrainer (2).
Embodiment 3:
In the multi-function extractor of 3000L, add 500 kilograms to be tea seed grouts and 1500 kilograms of ethanol that content is 70% of 2.5mm sieve through aperture, extract at normal temperatures 2 hours, after feed liquid separates with press filtration after filtration, filter residue in extractor carries out precipitation and recovery by hot steam, and the filtrate having entered in 2000L concentration tank concentrates the temperature of 80 DEG C, when the solid content in solution to be concentrated reaches 40%, obtain 150 kilograms of sasanguasaponin concentrated solutions, can directly use as air entrapment agent.
Embodiment 4:
The 150 kg of oil TS concentrated solutions and the 1.5 kilograms of industrial caustic soda that in the reactor of 500L, add embodiment 3 to make, after first dissolving with 30 premium on currency, 1.5 kilograms of industrial caustic soda add, at 110 DEG C of temperature, stir 50 minutes, obtain the hydrolysing oil TS shown in formula IV.
Embodiment 5:
In the multi-function extractor of 3000L, add 500 kilograms to be tea seed grouts and 1500 kilograms of methyl alcohol that content is 70% of 2.5mm sieve through aperture, extract at normal temperatures 2 hours, after feed liquid separates with press filtration after filtration, filter residue in extractor carries out precipitation and recovery by hot steam, and the filtrate having entered in 2000L concentration tank concentrates the temperature of 80 DEG C, when the solid content in solution to be concentrated reaches 40%, obtain 150 kilograms of sasanguasaponin concentrated solutions, can directly use as air entrapment agent.
Embodiment 6:
The sasanguasaponin concentrated solution and the 1.5 kilograms of industrial soda ash that in the reactor of 500L, add 150 kilograms of embodiment 5 to make, after first dissolving with 30 premium on currency, 1.5 kilograms of industrial soda ash add, at 110 DEG C of temperature, stir 50 minutes, then add 4.5 kilograms of triphenylmethyl chlorides, 3 kilograms of bromination 1-p-methylphenyl-2-diethyl hexadecyldimethyl benzyl ammonium-1-acetone, 6 kilogram 15% formic acid, at 180 DEG C of temperature, stir 2 hours, after cooling, obtain compd A, also can use as air entrapment agent.
Embodiment 7:
The product performance of reference product (the sasanguasaponin concrete air-entrainer that Shanghai Chinese ash Industrial Co., Ltd. produces) and the effect in concrete are with concrete concrete mix, the Performance Detection index of fresh mixing concrete property and maturing illustrates, experiment adopts 525 ordinary Portland cements: tap water: medium sand: rubble=350:144:567:1256(kg/m3) grating ratio, volume taking sasanguasaponin as air entrapment agent is 0.04% of cement consumption, mix 1.0% the ester type polycarboxylate high performance water-reducing agent of being produced by the Five Dragons, Zhejiang Chemical Co., Ltd. simultaneously, maximum aggregate size is 31.5mm.Result table one (1) and table one (2)
Table one (1), sasanguasaponin air entrapment agent the key technical indexes
| Outward appearance | Brown viscous liquid |
| Water-soluble | Dissolve completely |
| Surface tension | 32.6 MNs/m |
| Solid content | 38% |
| Foaming height (1.0% concentration, starting altitude) | 170 millimeters |
| Foam lost rate (1.0% concentration, 5 minutes) | 12.1% |
| PH value (1.0% concentration) | 5.4 |
Table one (2), the sasanguasaponin air entrapment agent property in concrete detects index
Remarks: sasanguasaponin air entrapment agent and ester type polycarboxylate high performance water-reducing agent compound tense have part oyster white material to separate out, and have partly precipitated to produce.
Embodiment 8:
The hydrolysing oil TS that product intermediate of the present invention is obtained by embodiment 4, be the product performance of basic hydrolysis type sasanguasaponin air entrapment agent, and effect in concrete is with concrete concrete mix, the Performance Detection index of fresh mixing concrete property and maturing illustrates, experiment adopts 525 ordinary Portland cements: tap water: medium sand: rubble=350:144:567:1256(kg/m3) grating ratio, the volume of basic hydrolysis type sasanguasaponin air entrapment agent is cement consumption 0.04%, mix simultaneously 1.0% by the Five Dragons, Zhejiang Chemical Co., Ltd. produce ester type polycarboxylate high performance water-reducing agent (by vinylformic acid, maleic anhydride, methacrylic acid, the binary that the grafted monomer such as Hydroxyethyl acrylate are polymerized or multiple copolymer), maximum aggregate size is 31.5mm.Result table two (1) and table two (2)
Table two (1), basic hydrolysis type sasanguasaponin air entrapment agent the key technical indexes
| Outward appearance | Brown viscous liquid |
| Water-soluble | Dissolve completely |
| Surface tension | 30.7 MNs/m |
| Solid content | 26% |
| Foaming height (1.0% concentration, starting altitude) | 182 millimeters |
| Foam lost rate (1.0% concentration, 5 minutes) | 9.2% |
| PH value (1.0% concentration) | 5.4 |
Table two (2), the basic hydrolysis type sasanguasaponin air entrapment agent property in concrete detects index
Remarks: basic hydrolysis type sasanguasaponin air entrapment agent is fewer than sasanguasaponin air entrapment agent with the oyster white material that ester type polycarboxylate high performance water-reducing agent compound tense is separated out, and the precipitation of generation is also less.
Embodiment 9:
The hydroxyl sequestered sasanguasaponin that product intermediate embodiment 6 of the present invention obtains, be compd A as the product performance of air entrapment agent and the effect in concrete with concrete concrete mix, the Performance Detection index of fresh mixing concrete property and maturing illustrates, experiment adopts 525 ordinary Portland cements: tap water: medium sand: rubble=350:144:567:1256(kg/m3) grating ratio, the volume of hydroxyl sequestered sasanguasaponin air entrapment agent is cement consumption 0.04%, mix 1.0% the ester type polycarboxylate high performance water-reducing agent of being produced by the Five Dragons, Zhejiang Chemical Co., Ltd. simultaneously, maximum aggregate size is 31.5mm.Result table three (1) and table three (2)
Table three (1), hydroxyl sequestered sasanguasaponin air entrapment agent the key technical indexes
| Outward appearance | Yellow viscous liquid |
| Water-soluble | Dissolve approximately 95% |
| Surface tension | 28.6 MNs/m |
| Solid content | 24% |
| Foaming height (1.0% concentration, starting altitude) | 178 millimeters |
| Foam lost rate (1.0% concentration, 5 minutes) | 9.6% |
| PH value (1.0% concentration) | 7.8 |
Table three (2), the hydroxyl sequestered sasanguasaponin air entrapment agent property in concrete detects index
Remarks: the oyster white material that hydroxyl sequestered sasanguasaponin air entrapment agent and ester type polycarboxylate high performance water-reducing agent compound tense are separated out is suitable with sasanguasaponin air entrapment agent, but precipitation is more than sasanguasaponin air entrapment agent.
Embodiment 10:
The product performance of the structural modification type cameclia oleifera saponin concrete air-entrainer (1) that product embodiments 1 of the present invention makes and the effect in concrete are with concrete concrete mix, the Performance Detection index of fresh mixing concrete property and maturing illustrates, experiment adopts 525 ordinary Portland cements: tap water: medium sand: rubble=350:144:567:1256(kg/m3) grating ratio, the volume of structural modification type cameclia oleifera saponin concrete air-entrainer (1) is cement consumption 0.04%, mix 1.0% the ester type polycarboxylate high performance water-reducing agent of being produced by the Five Dragons, Zhejiang Chemical Co., Ltd. simultaneously, maximum aggregate size is 31.5mm.Result table four (1) and table four (2)
Table four (1), structural modification type cameclia oleifera saponin concrete air-entrainer (1) the key technical indexes
| Outward appearance | Brown viscous liquid |
| Water-soluble | Dissolve completely |
| Surface tension | 25.4 MNs/m |
| Solid content | 28% |
| Foaming height (1.0% concentration, starting altitude) | 195 millimeters |
| Foam lost rate (1.0% concentration, 5 minutes) | 7.1% |
| PH value (1.0% concentration) | 7.6 |
(1 property in concrete detects index for table four (2), structural modification type cameclia oleifera saponin concrete air-entrainer
Remarks: structural modification type cameclia oleifera saponin concrete air-entrainer (1) and ester type polycarboxylate high performance water-reducing agent compound tense have no and separate out, precipitation and whiting.
Embodiment 11:
The product performance of the structural modification type cameclia oleifera saponin concrete air-entrainer (2) that product embodiments 2 of the present invention makes and the effect in concrete are with concrete concrete mix, the Performance Detection index of fresh mixing concrete property and maturing illustrates, experiment adopts 525 ordinary Portland cements: tap water: medium sand: rubble=350:144:567:1256(kg/m3) grating ratio, the volume of structural modification type cameclia oleifera saponin concrete air-entrainer (2) is cement consumption 0.04%, mix simultaneously 1.0% by the Five Dragons, Zhejiang Chemical Co., Ltd. produce ester type polycarboxylate high performance water-reducing agent (by vinylformic acid, maleic anhydride, methacrylic acid, the binary that the grafted monomer such as Hydroxyethyl acrylate are polymerized or multiple copolymer), maximum aggregate size is 31.5mm.Result table five (1) and table five (2)
Table five (1), structural modification type cameclia oleifera saponin concrete air-entrainer (2) the key technical indexes
| Outward appearance | Brown viscous liquid |
| Water-soluble | Dissolve completely |
| Surface tension | 25.1 MNs/m |
| Solid content | 26% |
| Foaming height (1.0% concentration, starting altitude) | 193 millimeters |
| Foam lost rate (1.0% concentration, 5 minutes) | 5.1 |
| PH value (1.0% concentration) | 7.8 |
Table five (2), structural modification type cameclia oleifera saponin concrete air-entrainer (2) property in concrete detects index
Remarks: structural modification type cameclia oleifera saponin concrete air-entrainer (2) and ester type polycarboxylate high performance water-reducing agent compound tense have no and separate out, precipitation and whiting, and consistency is better.
Embodiment 12:
The product performance of the structural modification type cameclia oleifera saponin concrete air-entrainer (2) that product embodiments 2 of the present invention makes and the effect in concrete are with concrete concrete mix, the Performance Detection index of fresh mixing concrete property and maturing illustrates, experiment adopts 525 ordinary Portland cements: tap water: medium sand: rubble=350:144:567:1256(kg/m3) grating ratio, the volume of structural modification type cameclia oleifera saponin concrete air-entrainer (2) is cement consumption 0.04%, mix 1.5% the naphthalene water reducer of being produced by Zhejiang Province Dadongwu Group Jianxin Material Co., Ltd (naphthene sulfonic acid-formaldehyde condensation products) simultaneously, maximum aggregate size is 31.5mm.Result table six (1) and table six (2)
Table six (1), structural modification type cameclia oleifera saponin concrete air-entrainer (2) the key technical indexes
| Outward appearance | Brown viscous liquid |
| Water-soluble | Dissolve completely |
| Surface tension | 25.1 MNs/m |
| Solid content | 26% |
| Foaming height (1.0% concentration, starting altitude) | 193 millimeters |
| Foam lost rate (1.0% concentration, 5 minutes) | 5.1 |
| PH value (1.0% concentration) | 7.8 |
Table six (2), structural modification type cameclia oleifera saponin concrete air-entrainer (2) property in concrete detects index
Remarks: structural modification type cameclia oleifera saponin concrete air-entrainer (2) and naphthalene water reducer (naphthene sulfonic acid-formaldehyde condensation products) compound tense have no and separate out, precipitation and whiting.
Embodiment 13:
The product performance of rosined soap class air entrapment agent and the effect in concrete are with concrete concrete mix, the Performance Detection index of fresh mixing concrete property and maturing illustrates, experiment adopts 525 ordinary Portland cements: tap water: medium sand: rubble=350:144:567:1256(kg/m3) grating ratio, the volume of AE-R colophony type concrete air-entrainer that Qingdao Xin Sheng building materials company limited produces is cement consumption 0.04%, mix simultaneously 1.5% by the Five Dragons, Zhejiang Chemical Co., Ltd. produce ester type polycarboxylate high performance water-reducing agent (by vinylformic acid, maleic anhydride, methacrylic acid, the binary that the grafted monomer such as Hydroxyethyl acrylate are polymerized or multiple copolymer), maximum aggregate size is 31.5mm.Result table seven (1) and table seven (2)
Table seven (1), rosined soap class air entrapment agent the key technical indexes
| Outward appearance | Brown viscous liquid |
| Water-soluble | Heating for dissolving |
| Surface tension | 38.5 MNs/m |
| Solid content | 33% |
| Foaming height (1.0% concentration, starting altitude) | 182 millimeters |
| Foam lost rate (1.0% concentration, 5 minutes) | 18.8 |
| PH value (1.0% concentration) | 9.5 |
Table seven (2), the rosined soap class air entrapment agent property in concrete detects index
Remarks: rosined soap class concrete air-entrainer and ester type polycarboxylate high performance water-reducing agent compound tense have that more oyster white material is separated out, deposited phenomenon is serious, and consistency is poor, is almost difficult to direct application.
Claims (6)
1. an intermediate for structural modification type cameclia oleifera saponin, described intermediate is the compd A as shown in formula II,
2. the preparation method of intermediate as claimed in claim 1, it is characterized in that described method is: get hydrolysing oil TS 100 mass parts shown in formula IV, triphenylmethyl chloride 1～5 mass parts, bromination 1-p-methylphenyl-2-diethyl hexadecyldimethyl benzyl ammonium-1-acetone 1～3 mass parts, 10～20% formic acid 1～6 mass parts, at 160～200 DEG C of temperature stirring reaction 2～3 hours, obtain the compd A shown in product formula II after cooling;
3. the preparation method of intermediate as claimed in claim 2, it is characterized in that the hydrolysing oil TS shown in described formula IV makes as follows: get the tea seed grouts particle that grain diameter is less than 2.5mm, taking mass concentration as 50%～80% alcoholic solvent, normal temperature dipping 1～3 hour, described alcoholic solvent was methyl alcohol or ethanol; Filter to obtain tea seed grouts extracting solution, abandon filter residue, described tea seed grouts extracting solution is concentrated under 50～100 DEG C of conditions, be concentrated into solid the containing while being 30～50% in enriched material, taking-up enriched material is sasanguasaponin, and adding quality is 5～15% caustic soda or soda ash of enriched material quality, and described caustic soda or soda ash add after with a small amount of water dissolution, under 100～120 DEG C of temperature condition, stir 30～60 minutes, obtaining extract is the hydrolysing oil TS shown in formula IV again.
Intermediate as claimed in claim 1 in preparation suc as formula the application in the structural modification type cameclia oleifera saponin shown in (I):
5. application as claimed in claim 4, the method that it is characterized in that described application is: get the compd B shown in the formula III of the compd A shown in the formula II of 3～5 mass parts and 2～3 mass parts, mix, add 0.5～1 mass parts methylene diethyl ether, stirring reaction 4～5 hours at 180～250 DEG C of temperature, be filled with hydrogen reducing again, remove unnecessary hydrogen, obtaining reduzate is the structural modification type cameclia oleifera saponin shown in formula (I);
Described compd B makes as follows: the sucrose of 5～10 mass parts is dissolved in the water of 100 parts, add the trimethyl orthoacetate of 2～5 mass parts, stirring reaction 1～2 hour at 150～180 DEG C of temperature, then add 2～5% dilute hydrochloric acid 1～3 mass parts, stirring reaction after 1～3 hour, adds 2～6% caustic soda again or soda ash 1～4 mass parts stirs 1～3 hour, finally add bromination 1-p-methylphenyl-2-diethyl hexadecyldimethyl benzyl ammonium-1-acetone 1～3 mass parts, 5～10% sodium methylate aqueous solution 4～5 mass parts, continue to stir 2～3 hours, obtain the compd B shown in product formula III,
6. intermediate as claimed in claim 1 is as the application of building concrete air entrapment agent.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1415570A (en) * | 2002-10-16 | 2003-05-07 | 同济大学 | Air entraining agent of triterpenoid saponin utilized in concrete work |
| CN1807333A (en) * | 2006-02-16 | 2006-07-26 | 江苏博特新材料有限公司 | Concrete air-entrainer |
| CN101497642A (en) * | 2009-03-19 | 2009-08-05 | 韶关学院 | Method for directly extracting tea saponin from tea seeds |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1415570A (en) * | 2002-10-16 | 2003-05-07 | 同济大学 | Air entraining agent of triterpenoid saponin utilized in concrete work |
| CN1807333A (en) * | 2006-02-16 | 2006-07-26 | 江苏博特新材料有限公司 | Concrete air-entrainer |
| CN101497642A (en) * | 2009-03-19 | 2009-08-05 | 韶关学院 | Method for directly extracting tea saponin from tea seeds |
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