CN111197062B - Modified plant tannin extract concrete air entraining agent and preparation method thereof - Google Patents
Modified plant tannin extract concrete air entraining agent and preparation method thereof Download PDFInfo
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- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
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Abstract
The invention discloses a modified plant tannin extract concrete air entraining agent and a preparation method thereof, wherein the molecular weight of the tannin extract is reduced through oxidative degradation and acid degradation, the tannin extract is modified through sulfitation, and then the modified plant tannin extract concrete air entraining agent is modified through grafting of allyl alcohol polyoxyethylene ether and sodium methacrylate, and a sulfonic group with foaming and air entraining effects and a polyether branched structure with air entraining and foam stabilizing effects are introduced, so that the modified plant tannin extract concrete air entraining agent is obtained. The modified plant tannin extract concrete air entraining agent prepared by the invention has the characteristics of good water solubility, strong foamability, fine foam stability, good compatibility with concrete systems and remarkable reinforcing and toughening effects, has good compatibility with water reducing agents, can be used for foaming and air entraining of concrete such as clean slurry, mortar, concrete and the like, has good compatibility with naphthalene water reducing agents and polycarboxylate water reducing agents, has small mixing amount, and has good foaming and air entraining effects.
Description
Technical Field
The invention belongs to the field of concrete additives, and particularly relates to a modified plant tannin extract concrete air entraining agent and a preparation method thereof.
Background
The concrete air entraining agent is an additive capable of introducing a large amount of tiny and uniform bubbles in the mixing process of concrete, and by introducing the bubbles with proper size and proper amount, the workability of the concrete mixture can be obviously improved, the construction performance such as slump loss can be reduced, and the strength, the durability such as freezing resistance, seepage resistance, carbonization resistance and the like of the hardened concrete can be improved. Under the condition that the basic components of the concrete are relatively stable, the performance of the used external agents such as air entraining agents and the like has important influence on the mixing performance and hardening performance of the concrete.
The common concrete air entraining agent is natural air entraining agent and synthetic air entraining agent. The natural air entraining agent mainly comprises rosin resin, triterpenoid saponin and the like, and the synthetic air entraining agent mainly comprises sodium alkyl sulfonate, sodium alkyl sulfate, sodium alkyl benzene sulfonate, fatty alcohol polyoxyethylene ether and the like. The synthetic air entraining agent has the advantages of more kinds and good air entraining effect, and the synthetic air entraining agent has the defects that the raw materials mainly depend on petrochemical products, the synthetic process has more steps and larger pollution. At present, the preparation of the concrete air entraining agent by means of modification of biomass materials is still an important research direction, and the modified natural material air entraining agent has the characteristics of renewable and environment-friendly main raw materials, environment-friendly preparation process, fine foam, stable foam, good compatibility with cement systems and the like.
Tannin extract is rich in polyphenol compounds in leaves, barks, stems, fruits and the like of some plants, is mainly used for leather tanning agents, but modified tannin extract has the defects of poor water solubility, deep color, easy mildew and the like, and is used as the leather tanning agent with little usage amount, so that new application of the tannin extract needs to be developed. The main component of tannin extract contains a large number of active groups such as phenolic hydroxyl groups, has certain wetting, penetrating and emulsifying effects, and has the problems of low water reducing rate, poor compatibility with polycarboxylic acid water reducing agents and the like when being modified into cement water reducing agents by someone. The tannin extract is used as a concrete air entraining agent by chemical and physical modification, and has the characteristics of good water solubility, strong foamability, fine foam stability, good compatibility with a concrete system, obvious reinforcing and toughening effects and the like.
Disclosure of Invention
The invention aims to provide a modified plant tannin extract concrete air entraining agent and a preparation method thereof, and the prepared modified plant tannin extract concrete air entraining agent has the characteristics of good water solubility, strong foamability, fine foam stability, good compatibility with concrete system, obvious reinforcing and toughening effects and the like.
In order to achieve the aim, the preparation method of the modified plant tannin extract concrete air entraining agent provided by the invention firstly reduces the molecular weight of the tannin extract through oxidative degradation and acid degradation, then carries out sulfitation modification on the tannin extract, and then carries out grafting modification on allyl alcohol polyoxyethylene ether and sodium methacrylate, thus obtaining the modified plant tannin extract concrete air entraining agent.
The method sequentially comprises the following steps of:
step one, oxidizing and degrading tannin extract:
60-80 parts of tannin extract is taken according to the parts by weight and dissolved in 200-250 parts of deionized water, 5.3-6.3 parts of hydrogen peroxide is added, the mixture is heated to 60-70 ℃ and degraded for 3.5-4.5 hours, and the oxidative degradation tannin extract is obtained;
step two, acid degradation tannin extract:
adding 5.3-7.5 parts of benzenesulfonic acid into the oxidative degradation tannin extract solution, heating to 70-80 ℃ and degrading for 3.0-3.5 hours to obtain an acid degradation tannin extract;
step three, sulfitation modified tannin extract:
the acid degradation tannin extract solution is kept at 30-40 ℃, 15.2-18.3 parts of sodium metabisulfite and 7.9-9.3 parts of formaldehyde solution are sequentially added, and stirring reaction is carried out for 4.5-5.5 hours, so that sulfurous acid modified tannin extract is obtained;
step four, grafting the modified tannin extract to prepare a modified plant tannin extract concrete air entraining agent:
23-28 parts of allyl alcohol polyoxyethylene ether and 5-8 parts of sodium methacrylate are added into the sulfitation modified tannin extract solution, the mixture is stirred and heated to 35-40 ℃, 5-8 parts of buffer solution is added to adjust the pH of the system to 6.5-7.0, 7-12 parts of horseradish peroxidase solution with the mass fraction of 0.08-0.16% and 16-21 parts of hydrogen peroxide solution with the mass fraction of 30% are simultaneously added dropwise, the dropwise adding time is controlled to be 1.5-2.0 hours, and the heat preservation reaction is continued for 4.5-5.5 hours after the dropwise adding is completed, so that the modified plant tannin extract concrete air entraining agent is obtained.
The tannin extract is one of oak extract, bayberry extract, wattle extract, larch extract, oil orange extract, herba Ephedrae extract, radix Aristolochiae extract, and chestnut extract.
The enzyme activity of the horseradish peroxidase is 330-u/mg, and the horseradish peroxidase with the mass fraction of 0.05-0.08 is dissolved in 50-60 parts of deionized water to prepare an aqueous solution with the mass fraction of 0.08-0.16%.
The preparation method of the buffer solution comprises the steps of dissolving 7.1-7.8 parts of sodium dihydrogen phosphate and 7.1-8.2 parts of disodium hydrogen phosphate in 100-110 parts of deionized water, and enabling the pH value to be 6.7-7.2.
The modified plant tannin extract concrete air entraining agent is prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
1) The natural high polymer material tannin extract is subjected to oxidative degradation and acid degradation in sequence to obtain a degraded tannin extract with proper molecular weight, hydrophilic groups such as hydroxyl, carboxyl and the like are generated in the degraded tannin extract structure in the degradation process, and the water solubility of the degraded tannin extract is improved; then the modified tannin extract is subjected to sulfitation modification and free radical graft polymerization modification with allyl alcohol polyoxyethylene ether and sodium methacrylate under enzyme catalysis, and polyether branched chains and sulfonic groups with dispersing, foaming, foam stabilizing and lubricating effects are introduced, so that the foaming, air entraining effects and the capability of stabilizing bubbles of the modified tannin extract are improved.
2) The invention takes tannin extract as a basic raw material, and prepares the modified tannin extract concrete air entraining agent through modification processes such as oxidative degradation, acid degradation, sulfitation, grafting of enzyme catalysis allyl alcohol polyoxyethylene ether and the like. The critical micelle concentration of the modified tannin extract air entraining agent is 0.158-0.193 mmol/L, the minimum value of the surface tension is 30.31-32.16 mN/m, the foam height reaches and is maintained at 126-129 mm within 30min, the introduced gas volume content is 3.3-4.6% when the doping amount in concrete is 0.015-0.021%, and the bubble diameter is mainly 50-160 mu m. The air entraining agent prepared by the method has good compatibility with the polycarboxylic acid water reducer and the naphthalene water reducer, the fluidity of the applied concrete is increased by 16-22%, the compressive strength is increased by 18-26%, and the durability parameter is improved by one grade.
3) The water reducer has good compatibility with water reducers, can be used for foaming and air entraining of concrete such as clean slurry, mortar and concrete, has good compatibility with naphthalene water reducers and polycarboxylate water reducers, has small mixing amount and has good foaming and air entraining effects.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but embodiments of the present invention include, but are not limited to, the scope of the following examples.
The invention provides a preparation method of a modified plant tannin extract concrete air entraining agent, which comprises the following specific steps of:
step one, oxidizing and degrading tannin extract: 60-80 parts of tannin extract is taken according to the parts by weight and dissolved in 200-250 parts of deionized water, 5.3-6.3 parts of hydrogen peroxide is added, the tannin extract is heated to 60-70 ℃ and degraded for 3.5-4.5 hours, and condensation components in the tannin extract are mainly degraded, so that the oxidative degradation tannin extract is obtained.
Step two, acid degradation tannin extract: 5.3-7.5 parts of benzenesulfonic acid is added into the oxidative degradation tannin extract solution, and the oxidative degradation tannin extract solution is heated to 70-80 ℃ for 3.0-3.5 hours, so that hydrolysis components in the tannin extract are mainly degraded, and the acid degradation tannin extract is obtained.
Step three, sulfitation modified tannin extract: and (3) maintaining the temperature of the acid degradation tannin extract solution at 30-40 ℃, sequentially adding 15.2-18.3 parts of sodium metabisulfite and 7.9-9.3 parts of formaldehyde solution, and stirring and reacting for 4.5-5.5 hours to obtain the sulfurous acid modified tannin extract.
Step four, grafting the modified tannin extract to prepare a modified tannin extract air entraining agent: 23-28 parts of allyl alcohol polyoxyethylene ether and 5-8 parts of sodium methacrylate are added into the sulfitation modified tannin extract solution, the mixture is stirred and heated to 35-40 ℃, 5-8 parts of buffer solution is added to adjust the pH of the system to 6.5-7.0, 7-12 parts of horseradish peroxidase solution with the mass fraction of 0.08-0.16% and 16-21 parts of hydrogen peroxide solution with the mass fraction of 30% are simultaneously added dropwise, the dropwise adding time is controlled to be 1.5-2.0 hours, and the heat preservation reaction is continued for 4.5-5.5 hours after the dropwise adding is completed, so that the modified tannin extract air entraining agent is obtained.
The tannin extracts are powder, and the content is more than 95%.
The hydrogen peroxide is a hydrogen peroxide water solution with the mass fraction of 30 percent.
The formaldehyde solution is 30% formaldehyde aqueous solution by mass fraction.
The allyl alcohol polyoxyethylene ether is APEG-1000, the appearance is white or yellowish solid, the hydroxyl value is 50-55 mgKOH/g, the pH value is 5.0-7.0, and the unsaturation degree is more than 0.9mmol/g.
The sodium methallyl sulfonate is white powder, and the content is more than 99%.
The preparation method of the buffer solution comprises the steps of dissolving 7.1-7.8 parts of sodium dihydrogen phosphate and 7.1-8.2 parts of disodium hydrogen phosphate in 100-110 parts of deionized water, and enabling the pH value to be 6.7-7.2.
The enzyme activity of the horseradish peroxidase is 330. 330 u/mg, and 0.05-0.08 part of horseradish peroxidase is accurately weighed and dissolved in 50-60 parts of deionized water to prepare an aqueous solution with the mass fraction of 0.08% -0.16%.
The relative molecular weight of the oxidative degradation tannin extract is 1300-5800.
The relative molecular mass of the acid degradation tannin extract is 500-1800.
The content of the sulfited acid groups in the sulfited modified tannin extract reaches 2.3-2.8%.
The conversion rate of the allyl alcohol polyoxyethylene ether grafted modified tannin extract reaches 96-99%. The grafting rate reaches 87-89%. The critical micelle concentration of the modified tannin extract air entraining agent is 0.158-0.193 mmol/L, the minimum value of surface tension is 30.31-32.16 mN/m, the foam height reaches 126-129 mm within 30 minutes, the introduced gas volume content is 3.3-4.6% when the mixing amount in concrete is 0.015-0.021% of the cement amount, and the bubble diameter is mainly 50-160 mu m. The air entraining agent prepared by the method has good compatibility with the polycarboxylic acid water reducer and the naphthalene water reducer, the fluidity of the applied concrete is increased by 16-22%, the compressive strength is increased by 18-26%, and the durability parameter is improved by one grade.
Example 1:
step one, oxidizing and degrading tannin extract, namely dissolving 60 parts of tannin extract in 200 parts of deionized water according to parts by weight, adding 5.3 parts of hydrogen peroxide, heating to 60 ℃, and degrading for 3.5 hours to obtain the oxidizing and degrading tannin extract.
And step two, acid degrading tannin extract, namely adding 5.3 parts of benzenesulfonic acid into the oxidative degradation tannin extract solution, heating to 70 ℃ and degrading for 3.0 hours to obtain the acid degradation tannin extract.
And thirdly, sulfitation modified tannin extract, wherein the acid degradation tannin extract solution is kept at 30 ℃, 15.2 parts of sodium metabisulfite and 7.9 parts of formaldehyde solution are sequentially added, and stirring reaction is carried out for 4.5 hours, so that the sulfurous acid modified tannin extract is obtained.
And fourthly, preparing a modified tannin extract air entraining agent by grafting the modified tannin extract, adding 23 parts of allyl alcohol polyoxyethylene ether and 5 parts of sodium methacrylate into the sulfitation modified tannin extract solution, stirring and heating to 35 ℃, adding 5 parts of buffer solution to adjust the pH of the system to 6.5, simultaneously dropwise adding 7 parts of horseradish peroxidase solution with the mass fraction of 0.08% and 16 parts of hydrogen peroxide solution with the mass fraction of 30%, controlling the dropwise adding time to be 1.5 hours, and continuing to perform heat preservation reaction for 4.5 hours after the dropwise adding is finished to obtain the modified tannin extract air entraining agent.
When the mixing amount of the concrete is 0.015% of the cement, the volume content of introduced gas is 3.3%, the diameter of bubbles is mainly 50 mu m, the fluidity of the applied concrete is increased by 16%, the compressive strength is increased by 18%, and the durability parameter is improved by one grade.
Example 2:
step one, oxidizing and degrading tannin extract, namely dissolving 80 parts of tannin extract in 250 parts of deionized water according to parts by weight, adding 6.3 parts of hydrogen peroxide, heating to 70 ℃ and degrading for 4.5 hours to obtain the oxidizing and degrading tannin extract.
And step two, acid degrading tannin extract, namely adding 7.5 parts of benzenesulfonic acid into the oxidative degradation tannin extract solution, heating to 80 ℃ and degrading for 3.5 hours to obtain the acid degradation tannin extract.
And thirdly, sulfitation modified tannin extract, wherein the acid degradation tannin extract solution is kept at 40 ℃, 18.3 parts of sodium metabisulfite and 9.3 parts of formaldehyde solution are sequentially added, and stirring reaction is carried out for 5.5 hours, so that the sulfurous acid modified tannin extract is obtained.
And fourthly, preparing a modified tannin extract air entraining agent by grafting the modified tannin extract, adding 28 parts of allyl alcohol polyoxyethylene ether and 8 parts of sodium methacrylate into the sulfitation modified tannin extract solution, stirring and heating to 40 ℃, adding 8 parts of buffer solution to adjust the pH of the system to 7.0, simultaneously dropwise adding 12 parts of horseradish peroxidase solution with the mass fraction of 0.16% and 21 parts of hydrogen peroxide solution with the mass fraction of 30%, controlling the dropwise adding time to be 2.0 hours, and continuing to perform heat preservation reaction for 5.5 hours after the dropwise adding is finished to obtain the modified tannin extract air entraining agent.
When the mixing amount in the concrete is 0.021% of the cement, the volume content of the introduced gas is 4.6%, the diameter of the air bubble is mainly 160 mu m, the fluidity of the applied concrete is increased by 22%, the compressive strength is increased by 26%, and the durability parameter is improved by one grade.
Example 3:
step one, oxidizing and degrading tannin extract, namely dissolving 65 parts of tannin extract in 220 parts of deionized water according to parts by weight, adding 5.8 parts of hydrogen peroxide, heating to 63 ℃ and degrading for 3.8 hours to obtain the oxidizing and degrading tannin extract.
And step two, acid degrading tannin extract, wherein 5.5 parts of benzenesulfonic acid is added into the oxidative degradation tannin extract solution, and the oxidative degradation tannin extract is obtained after the oxidative degradation tannin extract solution is heated to 72 ℃ and degraded for 3.2 hours.
And thirdly, sulfitation modified tannin extract, wherein the acid degradation tannin extract solution is kept at 33 ℃, 16.0 parts of sodium metabisulfite and 8.5 parts of formaldehyde solution are sequentially added, and stirring reaction is carried out for 4.8 hours, so that the sulfurous acid modified tannin extract is obtained.
And fourthly, preparing a modified tannin extract air entraining agent by grafting the modified tannin extract, adding 25 parts of allyl alcohol polyoxyethylene ether and 6 parts of sodium methacrylate into the sulfitation modified tannin extract solution, stirring and heating to 38 ℃, adding 6 parts of buffer solution to adjust the pH of the system to 6.6, simultaneously dropwise adding 9 parts of horseradish peroxidase solution with the mass fraction of 0.11% and 18 parts of hydrogen peroxide solution with the mass fraction of 30%, controlling the dropwise adding time to be 1.7 hours, and continuing to perform heat preservation reaction for 4.8 hours after the dropwise adding is finished to obtain the modified tannin extract air entraining agent.
When the mixing amount in the concrete is 0.018% of the cement amount, the introduced gas volume content is 3.8%, the bubble diameter is mainly 80 μm, the fluidity of the applied concrete is increased by 18%, the compressive strength is increased by 20%, and the durability parameter is improved by one grade.
Example 4:
step one, oxidizing and degrading tannin extract, namely dissolving 70 parts of tannin extract in 230 parts of deionized water according to parts by weight, adding 5.8 parts of hydrogen peroxide, heating to 66 ℃ and degrading for 4.2 hours to obtain the oxidizing and degrading tannin extract.
And step two, acid degradation tannin extract, wherein 7.0 parts of benzenesulfonic acid is added into the oxidative degradation tannin extract solution, and the solution is heated to 76 ℃ for 3.3 hours to obtain the acid degradation tannin extract.
And thirdly, sulfitation modified tannin extract, wherein the acid degradation tannin extract solution is kept at 36 ℃, 17.3 parts of sodium metabisulfite and 8.5 parts of formaldehyde solution are sequentially added, and stirring reaction is carried out for 5.2 hours, so that the sulfurous acid modified tannin extract is obtained.
And fourthly, preparing a modified tannin extract air entraining agent by grafting the modified tannin extract, adding 26 parts of allyl alcohol polyoxyethylene ether and 7 parts of sodium methacrylate into the sulfitation modified tannin extract solution, stirring and heating to 37 ℃, adding 7 parts of buffer solution to adjust the pH of the system to 6.8, simultaneously dropwise adding 9 parts of horseradish peroxidase solution with the mass fraction of 0.11% and 19 parts of hydrogen peroxide solution with the mass fraction of 30%, controlling the dropwise adding time to be 1.7 hours, and continuing to perform heat preservation reaction for 5.1 hours after the dropwise adding is finished to obtain the modified tannin extract air entraining agent.
When the mixing amount in the concrete is 0.018% of the cement, the introduced gas volume content is 4.2%, the bubble diameter is mainly 110 μm, the fluidity of the applied concrete is increased by 19%, the compressive strength is increased by 22%, and the durability parameter is improved by one grade.
Example 5:
step one, oxidizing and degrading tannin extract, namely dissolving 75 parts of tannin extract in 240 parts of deionized water according to parts by weight, adding 6.0 parts of hydrogen peroxide, heating to 68 ℃ and degrading for 4.3 hours to obtain the oxidizing and degrading tannin extract.
And step two, acid degrading tannin extract, namely adding 7.1 parts of benzenesulfonic acid into the oxidative degradation tannin extract solution, heating to 78 ℃ and degrading for 3.4 hours to obtain the acid degradation tannin extract.
And thirdly, sulfitation modified tannin extract, wherein the acid degradation tannin extract solution is kept at 38 ℃, 17.5 parts of sodium metabisulfite and 9.0 parts of formaldehyde solution are sequentially added, and stirring reaction is carried out for 5.3 hours, so that the sulfurous acid modified tannin extract is obtained.
And fourthly, preparing a modified tannin extract air entraining agent by grafting the modified tannin extract, adding 27 parts of allyl alcohol polyoxyethylene ether and 7 parts of sodium methacrylate into the sulfitation modified tannin extract solution, stirring and heating to 38 ℃, adding 7 parts of buffer solution to adjust the pH of the system to 6.8, simultaneously dropwise adding 11 parts of horseradish peroxidase solution with the mass fraction of 0.12% and 19 parts of hydrogen peroxide solution with the mass fraction of 30%, controlling the dropwise adding time to be 1.8 hours, and continuing to perform heat preservation reaction for 5.2 hours after the dropwise adding is finished to obtain the modified tannin extract air entraining agent.
When the mixing amount of the modified calcium carbonate is 0.019% of the cement amount, the introduced gas volume content is 4.1%, the bubble diameter is mainly 78 mu m, the fluidity of the applied concrete is increased by 21%, the compressive strength is increased by 24%, and the durability parameter is increased by one grade.
Among the above embodiments, embodiment 2 is the most preferred embodiment.
Claims (5)
1. A preparation method of a modified plant tannin extract concrete air entraining agent is characterized by comprising the following steps:
the method sequentially comprises the following steps of:
step one, oxidizing and degrading tannin extract:
60-80 parts of tannin extract is taken according to the parts by weight and dissolved in 200-250 parts of deionized water, 5.3-6.3 parts of hydrogen peroxide is added, the mixture is heated to 60-70 ℃ and degraded for 3.5-4.5 hours, and the oxidative degradation tannin extract is obtained;
step two, acid degradation tannin extract:
5.3-7.5 parts of benzenesulfonic acid is added into the oxidative degradation tannin extract solution, and the solution is heated to 70-80 ℃ and degraded for 3.0-3.5 hours to obtain an acid degradation tannin extract;
step three, sulfitation modified tannin extract:
the acid degradation tannin extract solution is kept at 30-40 ℃, 15.2-18.3 parts of sodium metabisulfite and 7.9-9.3 parts of formaldehyde solution are sequentially added, and stirring reaction is carried out for 4.5-5.5 hours, so that sulfurous acid modified tannin extract is obtained;
step four, grafting the modified tannin extract to prepare a modified plant tannin extract concrete air entraining agent:
23-28 parts of allyl alcohol polyoxyethylene ether and 5-8 parts of sodium methacrylate are added into the sulfitation modified tannin extract solution, the mixture is stirred and heated to 35-40 ℃, 5-8 parts of buffer solution is added to adjust the pH of the system to 6.5-7.0, 7-12 parts of horseradish peroxidase solution with the mass fraction of 0.08-0.16% and 16-21 parts of hydrogen peroxide solution with the mass fraction of 30% are simultaneously added dropwise, the dropwise adding time is controlled to be 1.5-2.0 hours, and the heat preservation reaction is continued for 4.5-5.5 hours after the dropwise adding is completed, so that the modified plant tannin extract concrete air entraining agent is obtained.
2. The method for preparing the modified plant tannin extract concrete air entraining agent according to claim 1, which is characterized in that:
the tannin extract is one of oak extract, bayberry extract, wattle extract, larch extract, oil orange extract, herba Ephedrae extract, radix Aristolochiae extract, and chestnut extract.
3. The method for preparing the modified plant tannin extract concrete air entraining agent according to claim 2, which is characterized in that:
the enzyme activity of the horseradish peroxidase is 330-u/mg, and the horseradish peroxidase with the mass fraction of 0.05-0.08 is dissolved in 50-60 parts of deionized water to prepare an aqueous solution with the mass fraction of 0.08-0.16%.
4. A method for preparing a modified plant tannin extract concrete air entraining agent according to claim 3, characterized in that:
the preparation method of the buffer solution comprises the steps of dissolving 7.1-7.8 parts of sodium dihydrogen phosphate and 7.1-8.2 parts of disodium hydrogen phosphate in 100-110 parts of deionized water, and enabling the pH value to be 6.7-7.2.
5. A modified plant extract concrete air entraining agent prepared by the preparation method of any one of claims 1 to 4.
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| CN101870990A (en) * | 2010-06-22 | 2010-10-27 | 陕西科技大学 | Method for synthesizing high molecular retanning dyeing auxiliary agents through enzyme catalysis |
| CN107548949A (en) * | 2017-09-27 | 2018-01-09 | 沈阳建筑大学 | A kind of low alkalinity gel material for concrete for plant growth and preparation method thereof |
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| CN101870990A (en) * | 2010-06-22 | 2010-10-27 | 陕西科技大学 | Method for synthesizing high molecular retanning dyeing auxiliary agents through enzyme catalysis |
| CN107548949A (en) * | 2017-09-27 | 2018-01-09 | 沈阳建筑大学 | A kind of low alkalinity gel material for concrete for plant growth and preparation method thereof |
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