CN102030801A - Structure modification type camellia saponin air entraining admixture as well as preparation method and application thereof - Google Patents
Structure modification type camellia saponin air entraining admixture as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a structure modification type camellia saponin disclosed as Formula (I), a preparation method of the structure modification type camellia saponin, and application and an application method of the structure modification type camellia saponin as a concrete air entraining admixture in architecture and engineering. The structure modification type camellia saponin in the invention used as an air entraining admixture has water solubility and favorable compounding property with other admixtures (especially with polycarboxylic acid water reducing agents or naphthalene water reducing agents), and overcomes the phenomena of sedimentation and precipitation when other air entraining admixtures are compounded with polycarboxylic acid water reducing agents or naphthalene water reducing agents.
Description
One, technical field
The present invention relates to a kind of novel structural modification type cameclia oleifera saponin and the air entrapment agent made from this structural modification type cameclia oleifera saponin, and their preparation method and application, structural modification type cameclia oleifera saponin provided by the invention is as the air entrapment agent in the material of construction concrete, can be widely used in hydro-structure, highway, road, bridge, building construction, underground structure is in commerical ready-mixed concrete that airfield runway etc. are nearly all and the onsite concrete engineering.
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 developed countries such as the U.S., Canada, Japan and Europe, 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 the 70-80% of concrete total amount, even more.
In China, remove the related standards regulation of water conservancy project structure, outside the necessary admixture bleed extremely of concrete, Other Engineering such as highway, road, bridge, building, underground structure, Important Project such as airfield runway all do not have regulation must mix air entrapment agent, therefore, in fact except that water conservancy project and northern harbour engineering, the little air entrapment agent of mixing of other Important Project.
Most of air entrapment agents are petrochemical compleies, system paper pulp, papermaking and some other industrial byproduct.At present the modal chemical composition of air entrapment agent has five classes: 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 early uses is representative with the rosined soap of introducing from USSR (Union of Soviet Socialist Republics), and the shortcoming of this air entrapment agent is to dissolve in hot water, to cause intensity to reduce bigger owing to introduce bubble, so has influenced the air entrapment agent application in the concrete works at home.Developed colophonium pyrolytic polymer afterwards and with washing composition, and drawn back the air entrapment agent of surfactant such as powder for the basis, solubility has been improved greatly, but that intensity reduces is still bigger.Up to the early 1990s, domestic traditional commodities air entrapment agent majority is the rosined soap type, minority colophonium pyrolytic polymer type product is also arranged, but also all there is unstable properties, poorly soluble, with the shortcoming of other admixture plyability differences, 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 shortcomings such as bigger, restricted applying of air entrapment agent.
U.S. home-made VINSOL colophonium pyrolytic polymer air entrapment agent, 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 objective of the invention is to propose a kind of stable performance, solvability is good, with high-performance water reducing agent of new generation---the poly carboxylic acid series water reducer composite effect is good, concrete strength is reduced little air entrapment agent and preparation technology thereof, to improve quality of concrete, 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) hydrolysis sasanguasaponin 100 mass parts shown in the modus ponens (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, under 160～200 ℃ of temperature stirring reaction 2～3 hours, promptly get the compd A shown in the product formula (II) after the cooling;
(2) sucrose of 5～10 mass parts is dissolved in 100 parts the water, add the trimethyl orthoacetate of 2～5 mass parts, stirring reaction 1～2 hour under 150～180 ℃ 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, add bromination 1-p-methylphenyl-2-diethyl hexadecyldimethyl benzyl ammonium-1-acetone 1～3 mass parts at last, 5～10% sodium methylate aqueous solution, 4～5 mass parts, continue to stir 2～3 hours, promptly get the compd B shown in the 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, the adding mass parts is 0.5～1 part a methylene diethyl ether, stirring reaction is 4～5 hours under 180～250 ℃ of temperature, charge into hydrogen reducing again, remove unnecessary hydrogen, promptly obtaining reduzate is the structural modification type cameclia oleifera saponin shown in the formula (I).
Hydrolysis sasanguasaponin shown in the formula (IV) also can be made air entrapment agent and use, but the air entrapment agent that the present invention proposes, main component is a structural modification type cameclia oleifera saponin, structural modification type cameclia oleifera saponin of the present invention refines acquisition from the 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 characteristics of poly carboxylic acid series water reducer, further optimize the 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 excellent, the good air entrapment agent product innovation of foaming properties that obtains with other admixture composite effect.
The present invention recommends the tea seed grouts directly to extract the 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 the tea seed grouts, from plant material, extract, pass through hydrolysis and a series of molecular structure alteration and other comprehensive technical measure then, obtain the hydrophilic midparent oil type in two, new air entraining product that foaming properties is good.The present invention recommends the hydrolysis sasanguasaponin shown in the following method preparation formula (IV): getting the tea seed grouts particle of grain diameter less than 2.5mm, is 50%～80% alcoholic solvent normal temperature dipping 1～3 hour with mass concentration, and described alcoholic solvent is methyl alcohol or ethanol; The amount of added alcoholic solvent is as the criterion below tea seed grouts particle is all immersed the alcoholic solvent liquid level, filter tea seed grouts extracting solution, filter residue in 50～100 ℃ of following precipitations in have the mass content of alcohol to be lower than and to emit at 1% o'clock to discard, the purpose of filter residue precipitation considers that mainly the alcohol of recovery can utilize again, and the filter residue that discards simultaneously is than environmental protection and can be used as utilizations such as fuel; Described tea seed grouts extracting solution concentrates under 50～100 ℃ of conditions, the solid content that is concentrated in the enriched material is 30～50% o'clock, take out enriched material and be sasanguasaponin, add quality and be 5～15% caustic soda or soda ash of enriched material quality, described caustic soda or soda ash add after with a spot of water dissolution, stirred 30～60 minutes under 100～120 ℃ of temperature condition, obtaining extract is the hydrolysis sasanguasaponin shown in the formula (IV) again; When adding caustic soda or soda ash, add behind dissolving caustic soda or the soda ash earlier with the water that is enough to dissolve caustic soda or soda ash usually, the implication of " on a small quantity " is meant and can allows caustic soda or the soda ash dissolved water yield just enough here, and this water yield can not allow other influence of reaction generation.
The present invention also provides the intermediate of described structural modification type cameclia oleifera saponin, suc as formula compd B shown in compd A shown in (II) and the formula (III).Provided by the present invention also is a kind of sasanguasaponin of modification suc as formula the compd A shown in (II), also can be used as concrete air entrapment agent and uses, and the embodiment of the 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, the methylene diethyl ether that adds 0.5～1 mass parts, stirring reaction is 4～5 hours under 180～250 ℃ of temperature, charge into hydrogen reducing again, remove unnecessary hydrogen, obtaining reduzate is the structural modification type cameclia oleifera saponin shown in the formula (I);
Described compd A makes as follows: hydrolysis sasanguasaponin 100 mass parts shown in the modus ponens (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, under 160～200 ℃ of temperature stirring reaction 2～3 hours, promptly get the compd A shown in the formula (II) after the cooling;
Described compd B makes as follows: the sucrose of 5～10 mass parts is dissolved in 100 parts the water, the trimethyl orthoacetate that adds 2～5 mass parts, stirring reaction is 1～2 hour under 150～180 ℃ of temperature, then add 2～5% dilute hydrochloric acid 1～3 mass parts, stirring reaction added 2～6% caustic soda or soda ash 1～4 mass parts stir about 1～3 hour again after 1～3 hour, add bromination 1-p-methylphenyl-2-diethyl hexadecyldimethyl benzyl ammonium-1-acetone 1～3 mass parts at last, 5～10% sodium methylate aqueous solution, 4～5 mass parts, continue to stir 2～3 hours, products therefrom is the compd B shown in the formula (III).Described compd B is to be used for the intermediate that the grafting addition uses.
Structural modification type cameclia oleifera saponin of the present invention can be used as the 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 the 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: when concrete batching, the structural modification type cameclia oleifera saponin that in concrete, adds cement quality 0.02～0.12% in the concrete foundation prescription, quality is the water reducer of cement quality 1～2% in the concrete foundation prescription, described water reducer is polycarboxylate high performance water-reducing agent or naphthalene water reducer, churning time was controlled at 2～4 minutes, carried out other operation of concrete preparation again.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 usually can be from commercially available.Naphthalene water reducer also can derive from commercially available.
When being re-used as the air entrapment agent use after the structural modification type cameclia oleifera saponin adding suds-stabilizing agent of the present invention, application method is: get described structural modification type cameclia oleifera saponin, adding suds-stabilizing agent A (propyl carbinol) stirred 1～2 hour with suds-stabilizing agent B (dimethyl dodecyl amine oxide), controlled temperature is to 60-80 ℃, drip and to add water to solid content and reach 20-25%, stir and make air entrapment agent, the ratio of described structural modification type cameclia oleifera saponin, suds-stabilizing agent A, suds-stabilizing agent B quality is 100: 1～3: 1～2; Described application method is: when concrete batching, described air entrapment agent, the quality that adds cement quality 0.02～0.12% in the concrete foundation prescription in concrete is the polycarboxylate high performance water-reducing agent of cement quality 1～2% in the concrete foundation prescription, churning time was controlled at 2～4 minutes, carried out other agitating procedure of concrete preparation again.Equally, the also available naphthalene water reducer of the polycarboxylate high performance water-reducing agent here substitutes, as naphthene sulfonic acid-formaldehyde condensation products.
Suds-stabilizing agent A of the present invention is a propyl carbinol, and suds-stabilizing agent B is a dimethyl dodecyl amine oxide.The said polycarboxylate high performance water-reducing agent of the present invention is binary or the multiple copolymer that is polymerized by grafted monomer such as vinylformic acid, maleic anhydride, methacrylic acid, Hydroxyethyl acrylates, and two types on ester type and ether type specifically arranged.
When using product of the present invention, recommend the mass ratio of cement, water, fine sand, rubble in the described concrete foundation prescription to be: 350: 140-160: 550-580: 1200-1300 (kg/m3) as air entrapment agent., preferred 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) getting the tea seed grouts particle of grain diameter less than 2.5mm, is 50%～80% alcoholic solvent normal temperature dipping 1～3 hour with mass concentration, and described alcoholic solvent is methyl alcohol or ethanol; Filter tea seed grouts extracting solution, filter residue 50～100 ℃ of following precipitations in have the mass content of alcohol to be lower than and to emit at 1% o'clock, tea seed grouts extracting solution concentrates under 50～100 ℃ of conditions, being concentrated into that consolidating in the enriched material contain is 30～50% o'clock, take out enriched material and be sasanguasaponin, add quality and be 5～15% caustic soda or soda ash of enriched material quality, described caustic soda or soda ash add after with a spot of water dissolution, stirred 30～60 minutes under 100～120 ℃ of temperature condition, obtaining extract is the hydrolysis sasanguasaponin shown in the 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%, under 160～200 ℃ of temperature stirring reaction 2～3 hours, promptly get the compd A shown in the formula (II) after the cooling;
(c) sucrose of 5～10 mass parts is dissolved in 100 parts the water, add the trimethyl orthoacetate of 2～5 mass parts, stirring reaction 1～2 hour under 150～180 ℃ of temperature, then add 2～5% dilute hydrochloric acid 1～3 mass parts, stirring reaction added the caustic soda of 2-6% or soda ash 1～4 mass parts stir about 1～3 hour again after 1～3 hour, add bromination 1-p-methylphenyl-2-diethyl hexadecyldimethyl benzyl ammonium-1-acetone 1～3 mass parts at last, 5～10% sodium methylate aqueous solution, 4～5 mass parts, continue to stir 2～3 hours, promptly get the compd B shown in the 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, the adding mass parts is 0.5～1 part a methylene diethyl ether, stirring reaction is 4～5 hours under 180～250 ℃ of temperature, charge into hydrogen reducing again, remove unnecessary hydrogen, promptly obtaining reduzate is the structural modification type cameclia oleifera saponin shown in the formula (I).
(e) get the reduzate that step (d) obtains, the adding mass parts is that the suds-stabilizing agent A and the suds-stabilizing agent B of reduzate 1～3% stirred 1-2 hour, when cooling to 60-80 ℃, drip water, when reaching 20-25% Deng solid content, promptly make described air entrapment agent, described suds-stabilizing agent A is a propyl carbinol, described suds-stabilizing agent B is a dimethyl dodecyl amine oxide, and the ratio of the reduzate that described step (d) obtains, suds-stabilizing agent A, suds-stabilizing agent B quality is 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, promptly have the organic compound of long chain molecule structure, and the one end contains hydrophilic radical; The other end contains the hydrophobic group.Though a large amount of triterpenoid saponin air entrapment agent foam exquisitenesses of discovering, but amount of air entrainment is less, use cost is higher, also falls into debt with the composite effect of poly carboxylic acid series water reducer simultaneously, in order to overcome above shortcoming, the contriver carries out molecular modification to its active ingredient structure, it is hydrophilic to make its final structure be modified into two, middle lipophilic new texture, and it is mainly by monosaccharide groups, glucoside key and glucoside unit base, compositions such as polysaccharide base.A lot of hydroxyls are arranged in monose and the polysaccharide, and (OH) can form hydrogen bond with water molecules, thereby have very strong wetting ability, be a hydrophilic radical; And the glucoside unit in the glucoside unit base has lipophilicity, is the hydrophobic group.Therefore structural modification type cameclia oleifera saponin is the amphipathic molecule that had not only contained hydrophilic radical but also contained the group of surging.After structural modification type cameclia oleifera saponin was water-soluble, molecule just aligned at gas--and on-liquid the interface, reduced 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, advantage and effect that the preparation concrete has are as follows:
(1) structural modification type cameclia oleifera saponin provided by the invention and to use the production technique of air entrapment agent of its preparation reasonable, product has extensive applicability in concrete works.
(2) concrete water-reducing ratio of air entrapment agent preparation provided by the invention is greater than 6%; Reach 8%
(3) the concrete water bleeding rate of air entrapment agent provided by the invention preparation drops to 8.6% by original 24.5%;
(4) the concrete concrete crushing strength rate of loss of air entrapment agent preparation provided by the invention, the ultimate compression strength loss that the per unit air content causes is less than 2%;
(5) concrete of air entrapment agent preparation provided by the invention, when air content was not more than 6%, concrete flexural strength can improve 10-30%;
(6) concrete of air entrapment agent preparation provided by the invention, frost resistance improves more than 8 times;
(7) the concrete deicer-scaling resistance raising of air entrapment agent preparation provided by the invention is more than 5 times;
(8) other weather resistance of concrete of air entrapment agent provided by the invention preparation such as salt crystallization crush badly, and alkali destruction etc. are also obviously improved;
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 the 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, specific embodiment
With specific embodiment technical scheme of the present invention is described below, but protection scope of the present invention is not limited thereto:
Embodiment 1
The first step: in the multi-function extractor of 3000L, adding 500 kilograms is that the tea seed grouts of 2.5mm sieve and 1500 kilograms of content are 70% methyl alcohol through the aperture, dipping extraction at normal temperatures 2 hours, feed liquid is after filtration with after press filtration separates, filter residue in the extractor carries out precipitation and recovery with hot steam, the filtrate that has entered in the 2000L concentration tank concentrates 3～4 hours 80 ℃ temperature, when the solid content in the solution to be concentrated reached for 40% (the concentrated solution quality is about 150 kilograms), concentrate pump is delivered in the reactor of 2000L with pressure pump, earlier with 1.5 kilograms of industrial caustic soda of 30 liters of pure water dissolvings, also add the dissolved caustic soda in the reactor again, stirred 50 minutes under 110 ℃ of temperature, getting product is the hydrolysis sasanguasaponin shown in the 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, under 180 ℃ of temperature, stirred 2 hours, getting product is compd A, and the cooling back is standby.
The 3rd step: in the reactor of 1000L, add 500 kilograms of tap water and 40 kilograms of sucrose, sucrose is after stirring dissolving fully, add 15 kilograms of trimethyl orthoacetates, and under 160 ℃ of temperature, stirred 1.5 hours, the dilute hydrochloric acid that then adds 10 kilogram 3%, continue to stir the caustic soda restir 1 hour that adds 15 kilogram 3% after 2 hours, adding 10 kilograms of bromination 1-p-methylphenyls-2-diethyl hexadecyldimethyl benzyl ammonium-1-acetone and 20 kilograms of concentration at last and be 8% the sodium methylate aqueous solution continues to stir 2 hours, getting product is compd B, and the cooling back is standby.
The 4th step: get second step of double centner gains and 50 kilogram of the 3rd step gains and in the reactor of 500L, mix, add 20 kilograms of methylene diethyl ethers, under 200 ℃ of temperature, stirred 5 hours, charge into 10L hydrogen again in mixture, after 1 hour, remove unnecessary hydrogen, promptly get the structural modification type cameclia oleifera saponin shown in the formula (I), abbreviate structural modification type cameclia oleifera saponin concrete air-entrainer (1) as.
Embodiment 2:
The first step: in the multi-function extractor of 3000L, adding 500 kilograms is that the tea seed grouts of 2.5mm sieve and 1500 kilograms of content are 70% methyl alcohol through the aperture, extracted at normal temperatures 2 hours, feed liquid is after filtration with after press filtration separates, filter residue in the extractor carries out precipitation and recovery with hot steam, the filtrate that has entered in the 2000L concentration tank concentrates 3～4 hours 80 ℃ temperature, when the solid content in the solution to be concentrated reached for 40% (the concentrated solution quality is about 150 kilograms), concentrate pump is delivered in the reactor of 2000L with pressure pump, earlier with 1.5 kilograms of industrial soda ash of 30 liters of pure water dissolvings, again dissolved soda ash is added in the reactor, after stirring 50 minutes under 110 ℃ of temperature, 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, under 180 ℃ of temperature, stirred 2 hours, getting product is compd A, and the cooling back is standby.
Second step: in the reactor of 1000L, add 500 kilograms of tap water and 40 kilograms of sucrose, sucrose is after stirring dissolving fully, add 15 kilograms of trimethyl orthoacetates, and under 160 ℃ of temperature, stirred 1.5 hours, the dilute hydrochloric acid that then adds 10 kilogram 3%, continue to stir the soda ash restir 1 hour that adds 8 kilogram 3% after 2 hours, adding 10 kilograms of bromination 1-p-methylphenyls-2-diethyl hexadecyldimethyl benzyl ammonium-1-acetone and 20 kilograms of concentration at last and be 8% the sodium methylate aqueous solution continues to stir 2 hours, getting product is compd B, and the cooling back is standby.
The 3rd step: get double centner the first step gains and 50 kilogram second step gains and in the reactor of 500L, mix, add 20 kilograms of methylene diethyl ethers, under 200 ℃ of temperature, stirred 5 hours, charge into 10L hydrogen again in mixture, after 1 hour, remove unnecessary hydrogen, promptly get the structural modification type cameclia oleifera saponin shown in the formula (I); Continuation adds 2 kilograms of propyl carbinols again and 1.5 kilograms of dimethyl dodecyl amine oxides stirred 1 hour, when cooling to 60 ℃, drips tap water, waits solid content to reach at 25% o'clock, can make the concrete air-entrainer that contains structural modification type cameclia oleifera saponin.Abbreviate structural modification type cameclia oleifera saponin concrete air-entrainer (2) as.
Embodiment 3:
In the multi-function extractor of 3000L, adding 500 kilograms is that the tea seed grouts of 2.5mm sieve and 1500 kilograms of content are 70% ethanol through the aperture, extracted at normal temperatures 2 hours, feed liquid is after filtration with after press filtration separates, filter residue in the extractor carries out precipitation and recovery with hot steam, and the filtrate that has entered in the 2000L concentration tank is concentrated 80 ℃ temperature, and the solid content in the solution to be concentrated reaches at 40% o'clock, promptly get 150 kilograms of sasanguasaponin concentrated solutions, can directly use as air entrapment agent.
Embodiment 4:
In the reactor of 500L, add 150 kilograms of sasanguasaponin concentrated solutions and 1.5 kilograms of industrial caustic soda that embodiment 3 makes, 1.5 the industrial caustic soda of kilogram adds with 30 premium on currency dissolving back earlier, under 110 ℃ of temperature, stirred 50 minutes, promptly get the hydrolysis sasanguasaponin shown in the formula (IV).
Embodiment 5:
In the multi-function extractor of 3000L, adding 500 kilograms is that the tea seed grouts of 2.5mm sieve and 1500 kilograms of content are 70% methyl alcohol through the aperture, extracted at normal temperatures 2 hours, feed liquid is after filtration with after press filtration separates, filter residue in the extractor carries out precipitation and recovery with hot steam, and the filtrate that has entered in the 2000L concentration tank is concentrated 80 ℃ temperature, and the solid content in the solution to be concentrated reaches at 40% o'clock, promptly get 150 kilograms of sasanguasaponin concentrated solutions, can directly use as air entrapment agent.
Embodiment 6:
In the reactor of 500L, add 150 kilograms of sasanguasaponin concentrated solution and 1.5 kilograms of industrial soda ash that embodiment 5 makes, 1.5 the industrial soda ash of kilogram adds with 30 premium on currency dissolving back earlier, under 110 ℃ of temperature, stirred 50 minutes, add then 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, under 180 ℃ of temperature, stirred 2 hours, promptly get compd A after the cooling, 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, 525 ordinary Portland cements are adopted in experiment: tap water: medium sand: rubble=350: 144: 567: 1256 (kg/m3) level mixing ratio, is 0.04% of cement consumption with sasanguasaponin as the volume of air entrapment agent, mix 1.0% the ester type polycarboxylate high performance water-reducing agent by the production of the Five Dragons, Zhejiang chemical industry company limited simultaneously, maximum aggregate size is 31.5mm.
Table one (1) and table one (2) as a result
Table one (1), sasanguasaponin air entrapment agent the key technical indexes
| Outward appearance | The brown viscous liquid |
| Water-soluble | Dissolving fully |
| Surface tension | 32.6 milli ox/rice |
| 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 detection index in concrete
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 hydrolysis sasanguasaponin 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 the effect in concrete is with concrete concrete mix, the Performance Detection index of fresh mixing concrete property and maturing illustrates, 525 ordinary Portland cements are adopted in experiment: tap water: medium sand: rubble=350: 144: 567: 1256 (kg/m3) level mixing ratio, the volume of basic hydrolysis type sasanguasaponin air entrapment agent is 0.04% of a cement consumption, mix 1.0% the ester type polycarboxylate high performance water-reducing agent of producing by the Five Dragons, Zhejiang chemical industry company limited simultaneously (by vinylformic acid, maleic anhydride, methacrylic acid, binary that grafted monomer such as Hydroxyethyl acrylate are polymerized or multiple copolymer), maximum aggregate size is 31.5mm.Table two (1) and table two (2) as a result
Table two (1), basic hydrolysis type sasanguasaponin air entrapment agent the key technical indexes
| Outward appearance | The brown viscous liquid |
| Water-soluble | Dissolving fully |
| Surface tension | 30.7 milli ox/rice |
| 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 detection index in concrete
Remarks: basic hydrolysis type sasanguasaponin air entrapment agent lacks than the 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 that product intermediate embodiment 6 of the present invention the obtains type sasanguasaponin that dissociates, 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, 525 ordinary Portland cements are adopted in experiment: tap water: medium sand: rubble=350: 144: 567: 1256 (kg/m3) level mixing ratio, the volume of the free type sasanguasaponin air entrapment agent of hydroxyl is 0.04% of a cement consumption, mix 1.0% the ester type polycarboxylate high performance water-reducing agent by the production of the Five Dragons, Zhejiang chemical industry company limited simultaneously, maximum aggregate size is 31.5mm.Table three (1) and table three (2) as a result
Table three (1), the free type sasanguasaponin air entrapment agent the key technical indexes of hydroxyl
| Outward appearance | Yellow viscous liquid |
| Water-soluble | Dissolve about 95% |
| Surface tension | 28.6 milli ox/rice |
| 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 free property detection index of type sasanguasaponin air entrapment agent in concrete of hydroxyl
Remarks: the oyster white material that free type sasanguasaponin air entrapment agent of hydroxyl and ester type polycarboxylate high performance water-reducing agent compound tense are separated out is suitable with the sasanguasaponin air entrapment agent, but precipitation is more than the 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, 525 ordinary Portland cements are adopted in experiment: tap water: medium sand: rubble=350: 144: 567: 1256 (kg/m3) level mixing ratio, the volume of structural modification type cameclia oleifera saponin concrete air-entrainer (1) is 0.04% of a cement consumption, mix 1.0% the ester type polycarboxylate high performance water-reducing agent by the production of the Five Dragons, Zhejiang chemical industry company limited simultaneously, maximum aggregate size is 31.5mm.Table four (1) and table four (2) as a result
Table four (1), structural modification type cameclia oleifera saponin concrete air-entrainer (1) the key technical indexes
| Outward appearance | The brown viscous liquid |
| Water-soluble | Dissolving fully |
| Surface tension | 25.4 milli ox/rice |
| 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 |
Table four (2), structural modification type cameclia oleifera saponin concrete air-entrainer (1 property detection index in concrete
Remarks: structural modification type cameclia oleifera saponin concrete air-entrainer (1) and ester type polycarboxylate high performance water-reducing agent compound tense do not see 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, 525 ordinary Portland cements are adopted in experiment: tap water: medium sand: rubble=350: 144: 567: 1256 (kg/m3) level mixing ratio, the volume of structural modification type cameclia oleifera saponin concrete air-entrainer (2) is 0.04% of a cement consumption, mix 1.0% the ester type polycarboxylate high performance water-reducing agent of producing by the Five Dragons, Zhejiang chemical industry company limited simultaneously (by vinylformic acid, with come acid anhydrides, methacrylic acid, binary that grafted monomer such as Hydroxyethyl acrylate are polymerized or multiple copolymer), maximum aggregate size is 31.5mm.Table five (1) and table five (2) as a result
Table five (1), structural modification type cameclia oleifera saponin concrete air-entrainer (2) the key technical indexes
| Outward appearance | The brown viscous liquid |
| Water-soluble | Dissolving fully |
| Surface tension | 25.1 milli ox/rice |
| 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) the property detection index in concrete
Remarks: structural modification type cameclia oleifera saponin concrete air-entrainer (2) and ester type polycarboxylate high performance water-reducing agent compound tense do not see separate out, precipitation and whiting, 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, 525 ordinary Portland cements are adopted in experiment: tap water: medium sand: rubble=350: 144: 567: 1256 (kg/m3) level mixing ratio, the volume of structural modification type cameclia oleifera saponin concrete air-entrainer (2) is 0.04% of a cement consumption, mix 1.5% the naphthalene water reducer (naphthene sulfonic acid-formaldehyde condensation products) by Zhejiang Province Dadongwu Group Jianxin Material Co., Ltd's production simultaneously, maximum aggregate size is 31.5mm.Table six (1) and table six (2) as a result
Table six (1), structural modification type cameclia oleifera saponin concrete air-entrainer (2) the key technical indexes
| Outward appearance | The brown viscous liquid |
| Water-soluble | Dissolving fully |
| Surface tension | 25.1 milli ox/rice |
| 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) the property detection index in concrete
Remarks: structural modification type cameclia oleifera saponin concrete air-entrainer (2) and naphthalene water reducer (naphthene sulfonic acid-formaldehyde condensation products) compound tense do not see 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, 525 ordinary Portland cements are adopted in experiment: tap water: medium sand: rubble=350: 144: 567: 1256 (kg/m3) level mixing ratio, the volume of the AE-R colophony type concrete air-entrainer that Qingdao prosperous Sheng building materials company limited produces is 0.04% of a cement consumption, mix 1.5% the ester type polycarboxylate high performance water-reducing agent of producing by the Five Dragons, Zhejiang chemical industry company limited simultaneously (by vinylformic acid, maleic anhydride, methacrylic acid, binary that grafted monomer such as Hydroxyethyl acrylate are polymerized or multiple copolymer), maximum aggregate size is 31.5mm.Table seven (1) and table seven (2) as a result
Table seven (1), rosined soap class air entrapment agent the key technical indexes
| Outward appearance | The brown viscous liquid |
| Water-soluble | Heating for dissolving |
| Surface tension | 38.5 milli ox/rice |
| 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 detection index in concrete
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 relatively poor, almost is difficult to direct application.
Claims (10)
1. one kind suc as formula the structural modification type cameclia oleifera saponin shown in (I),
2. structural modification type cameclia oleifera saponin as claimed in claim 1 is characterized in that, described structural modification type cameclia oleifera saponin makes as follows:
(1) hydrolysis sasanguasaponin 100 mass parts shown in the modus ponens (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, under 160～200 ℃ of temperature stirring reaction 2～3 hours, promptly get the compd A shown in the product formula (II) after the cooling;
(2) sucrose of 5～10 mass parts is dissolved in 100 parts the water, add the trimethyl orthoacetate of 2～5 mass parts, stirring reaction 1～2 hour under 150～180 ℃ 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, add bromination 1-p-methylphenyl-2-diethyl hexadecyldimethyl benzyl ammonium-1-acetone 1～3 mass parts at last, 5～10% sodium methylate aqueous solution, 4～5 mass parts, continue to stir 2～3 hours, promptly get the compd B shown in the product formula (III);
(3) get the product and 2～3 mass parts step (2) products therefroms of 3～5 mass parts step (1) gained, mix, the adding mass parts is 0.5～1 part a methylene diethyl ether, stirring reaction is 4～5 hours under 180～250 ℃ of temperature, charge into hydrogen reducing again, remove unnecessary hydrogen, promptly obtaining reduzate is the structural modification type cameclia oleifera saponin shown in the formula (I).
3. the intermediate of a structural modification type cameclia oleifera saponin as claimed in claim 1, structural formula is suc as formula the compd A shown in (II).
4. the intermediate of a structural modification type cameclia oleifera saponin as claimed in claim 1, structural formula is suc as formula the compd B shown in (III).
5. the preparation method of a structural modification type cameclia oleifera saponin as claimed in claim 1 is characterized in that described method carries out as follows:
Get the compd A and 2～3 mass parts compd Bs of 3～5 mass parts, mix, add 0.5～1 mass parts methylene diethyl ether, stirring reaction is 4～5 hours under 180～250 ℃ of temperature, charge into hydrogen reducing again, remove unnecessary hydrogen, obtaining reduzate is the structural modification type cameclia oleifera saponin shown in the formula (I); Described compd A makes as follows: hydrolysis sasanguasaponin 100 mass parts shown in the modus ponens (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, under 160～200 ℃ of temperature stirring reaction 2～3 hours, promptly get the compd A shown in the product formula (II) after the cooling;
Described compd B makes as follows: the sucrose of 5～10 mass parts is dissolved in 100 parts the water, the trimethyl orthoacetate that adds 2～5 mass parts, stirring reaction is 1～2 hour under 150～180 ℃ of temperature, then add 2～5% dilute hydrochloric acid 1～3 mass parts, stirring reaction added 2～6% caustic soda or soda ash 1～4 mass parts stir about 1～3 hour again after 1～3 hour, add bromination 1-p-methylphenyl-2-diethyl hexadecyldimethyl benzyl ammonium-1-acetone 1～3 mass parts at last, 5～10% sodium methylate aqueous solution, 4～5 mass parts, continue to stir 2～3 hours, promptly get the compd B shown in the product formula (III).
6. the preparation method of structural modification type cameclia oleifera saponin as claimed in claim 5, it is characterized in that the hydrolysis sasanguasaponin shown in the described formula (IV) makes as follows: get the tea seed grouts particle of grain diameter less than 2.5mm, with mass concentration is 50%～80% alcoholic solvent normal temperature dipping 1～3 hour, and described alcoholic solvent is methyl alcohol or ethanol; Filter tea seed grouts extracting solution, abandon filter residue, described tea seed grouts extracting solution concentrates under 50～100 ℃ of conditions, being concentrated into that consolidating in the enriched material contain is 30～50% o'clock, the taking-up enriched material is a sasanguasaponin, adds quality and be 5～15% caustic soda or soda ash of enriched material quality, and described caustic soda or soda ash add after with a spot of water dissolution, stirred 30～60 minutes under 100～120 ℃ of temperature condition, obtaining extract is the hydrolysis sasanguasaponin shown in the formula (IV) again.
7. structural modification type cameclia oleifera saponin as claimed in claim 1 is characterized in that described being applied as the application of building concrete air entrapment agent, in preparation during cement concrete, directly with described structural modification type cameclia oleifera saponin as air entrapment agent; Described application method is as follows: when concrete batching, structural modification type cameclia oleifera saponin, the quality that adds cement quality 0.02～0.12% in the concrete foundation prescription in concrete is the water reducer of cement quality 1～2% in the concrete foundation prescription, described water reducer is polycarboxylate high performance water-reducing agent or naphthalene water reducer, churning time was controlled at 2～4 minutes, carried out other agitating procedure of concrete preparation again.
8. structural modification type cameclia oleifera saponin as claimed in claim 1 is as the application of building concrete air entrapment agent, it is characterized in that described being applied as: get described structural modification type cameclia oleifera saponin, adding suds-stabilizing agent A and suds-stabilizing agent B stirred 1～2 hour, controlled temperature is to 60-80 ℃, drip and to add water to solid content and reach 20-25%, stir and make air entrapment agent earlier, the ratio of described structural modification type cameclia oleifera saponin, suds-stabilizing agent A, suds-stabilizing agent B quality is 100: 1～3: 1～2; Described suds-stabilizing agent A is a propyl carbinol, described suds-stabilizing agent B is a dimethyl dodecyl amine oxide, described application method is: when concrete batching, described air entrapment agent, the quality that adds cement quality 0.02～0.12% in the concrete foundation prescription in concrete is the water reducer of cement quality 1～2% in the concrete foundation prescription, described water reducer is polycarboxylate high performance water-reducing agent or naphthalene water reducer, churning time was controlled at 2～4 minutes, carried out other operation of concrete preparation again.
9. as claim 7 or 8 described application, it is characterized in that the mass ratio of cement, water, fine sand, rubble in the described concrete foundation prescription is: 350: 140-160: 550-580: 1200-1300.
10. building concrete air entrapment agent that contains structural modification type cameclia oleifera saponin, described air entrapment agent makes as follows:
(a) getting the tea seed grouts particle of grain diameter less than 2.5mm, is 50%～80% alcoholic solvent normal temperature dipping 1～3 hour with mass concentration, and described alcoholic solvent is methyl alcohol or ethanol; Filter tea seed grouts extracting solution, abandon filter residue, described tea seed grouts extracting solution concentrates under 50～100 ℃ of conditions, being concentrated into that consolidating in the enriched material contain is 30～50% o'clock, take out enriched material and be sasanguasaponin, adding quality is the caustic soda or the soda ash of enriched material quality 5～15%, and described caustic soda or soda ash add after with a spot of water dissolution, stirred 30～60 minutes under 100～120 ℃ of temperature condition, obtaining extract is the hydrolysis sasanguasaponin shown in the 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%, under 160～200 ℃ of temperature stirring reaction 2～3 hours, promptly get the compd A shown in the product formula (II) after the cooling;
(c) sucrose of 5～10 mass parts is dissolved in 100 parts the water, add the trimethyl orthoacetate of 2～5 mass parts, stirring reaction 1～2 hour under 150～180 ℃ of temperature, then add 2～5% dilute hydrochloric acid 1～3 mass parts, stirring reaction added the caustic soda of 2-6% or soda ash 1～4 mass parts stir about 1～3 hour again after 1～3 hour, add bromination 1 p-methylphenyl-2-diethyl hexadecyldimethyl benzyl ammonium-1-acetone 1～3 mass parts at last, 5～10% sodium methylate aqueous solution, 4～5 mass parts, continue to stir 2～3 hours, promptly get the compd B shown in the product formula (III);
(d) get the product and 2～3 mass parts step (c) products therefroms of 3～5 mass parts step (b) gained, mix, the adding mass parts is 0.5～1 part a methylene diethyl ether, stirring reaction is 4～5 hours under 180～250 ℃ of temperature, charge into hydrogen reducing again, remove unnecessary hydrogen, promptly obtaining reduzate is the structural modification type cameclia oleifera saponin shown in the formula (I).
(e) get the reduzate that step (d) obtains, adding mass parts is the suds-stabilizing agent A and the suds-stabilizing agent B of reduzate 1～3%, stirred 1-2 hour, when cooling to 60-80 ℃, drip water, when waiting solid content to reach 20-25%, promptly make described air entrapment agent, described suds-stabilizing agent A is a propyl carbinol, and described suds-stabilizing agent B is a dimethyl dodecyl amine oxide, and the ratio of the reduzate that described step (d) obtains, suds-stabilizing agent A, suds-stabilizing agent B quality is 100: 1～3: 1～2.
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| CN102408200A (en) * | 2011-08-22 | 2012-04-11 | 青田中野天然植物科技有限公司 | Camellia saponin modified composite concrete air entraining agent |
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| CN102408200A (en) * | 2011-08-22 | 2012-04-11 | 青田中野天然植物科技有限公司 | Camellia saponin modified composite concrete air entraining agent |
| CN103466984A (en) * | 2013-09-02 | 2013-12-25 | 福州大学 | Sasanqua saponin concrete air entraining agent and preparation method thereof |
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| CN111116844B (en) * | 2020-01-18 | 2022-01-25 | 广东汇强外加剂有限公司 | Air-entraining type polycarboxylate superplasticizer and preparation method thereof |
| CN114644679A (en) * | 2020-12-18 | 2022-06-21 | 百极优棠(广东)医药科技有限公司 | Glucuronic acid glucoside compound, preparation method and application thereof |
| CN114644679B (en) * | 2020-12-18 | 2024-01-09 | 百极优棠(广东)医药科技有限公司 | Glucuronide compound, preparation method and application thereof |
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