CN112608479B - Low-viscosity modifier - Google Patents
Low-viscosity modifier Download PDFInfo
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- CN112608479B CN112608479B CN201911114515.3A CN201911114515A CN112608479B CN 112608479 B CN112608479 B CN 112608479B CN 201911114515 A CN201911114515 A CN 201911114515A CN 112608479 B CN112608479 B CN 112608479B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/40—Compounds containing silicon, titanium or zirconium or other organo-metallic compounds; Organo-clays; Organo-inorganic complexes
- C04B24/42—Organo-silicon compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/918—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/44—Thickening, gelling or viscosity increasing agents
Abstract
The invention discloses a low-viscosity modifier which can effectively reduce the initial viscosity of high-grade concrete, improve the fluidity, obviously improve the viscosity of the high-grade concrete after the concrete loses with time and effectively improve the fluidity of the concrete.
Description
Technical Field
The invention relates to the technical field of building materials, in particular to a low-viscosity modifier.
Background
With the continuous development of the concrete industry in China, the urban and rural integration progress is continuously accelerated, and the concrete is required to be developed towards the directions of environmental protection, high performance, high quality, high strength and the like. The concrete with the strength grade from ordinary strength C25 to ultrahigh strength C120 is increased along with the increase of the strength grade, the cement consumption in the concrete is increased, and the concrete has higher requirements on various raw materials such as sand, stone, additives and the like. In high-performance and high-strength concrete, when the cement consumption is increased and the water consumption is relatively reduced, a concrete system becomes relatively 'dead plate', the problems of poor flowing performance and the like can increase the difficulty of site construction. The concrete fluidity requirement is high especially for pipelines, pumping concrete and the like. When the strength grade of the concrete is too high, the concrete pumping is not facilitated under the condition that a concrete system is viscous. In addition, even if the concrete is added with additives such as a retarding water reducing agent and the like under the conditions of long-distance transportation and high temperature in summer, the concrete can also show the conditions of 'stiffness', poor flowing property and the like, and great difficulty is brought to site construction.
In conclusion, the factors of high strength, large cement consumption, low water-cement ratio, poor sand-gravel gradation, environment and the like can increase the viscosity of a concrete system, the field construction is very inconvenient, and the low-viscosity modifier is one of the problems which are urgently needed to be solved by a plurality of concrete research workers at present, so the low-viscosity modifier plays an important role in high-grade concrete.
Disclosure of Invention
The low-viscosity modifier disclosed by the invention can effectively reduce the initial viscosity of high-grade concrete, improve the fluidity, obviously improve the viscosity of the high-grade concrete after the concrete loses with time, and effectively improve the fluidity of the concrete.
The invention is realized by adopting the following scheme:
a low viscosity modifier comprising a compound of the formula:
wherein R is1Is H or CH3M is 3 to 13, wherein R2Is H, CH3、COOH，R3Is COOH, COOCH3，n＝5～20。
Preferably, the preparation method of the low-viscosity modifier comprises the steps of hydrogenating unsaturated polyester resin to obtain saturated polyester resin, and then reacting the obtained saturated polyester resin with silane coupling agent, emulsifier and carbonate to obtain the target compound.
More preferably, the preparation method of the low viscosity modifier further comprises reacting the diol oligomer with an unsaturated carboxylic acid to obtain an unsaturated polyester resin.
More preferably, the diol oligomer has the following structure:
wherein R is1Is H or CH3When R is1When the number is H, m is 4-13; when R is1Is CH3When m is 5 to 20.
More preferably, the unsaturated acid has the following structural formula:
wherein R is2H, CH3, COOH, R3COOH, COOCH 3; when R is2＝H，R3COOH, acrylic acid; when R is2＝CH3，R3COOH methacrylic acid; when R is2＝COOH，R3COOH is fumaric acid; when R is2＝H，R3＝COOCH3Is methyl acrylate; r2＝CH3，R3＝COOCH3Is methyl methacrylate.
More preferably, the diol oligomer and the unsaturated carboxylic acid are reacted in an inorganic acid environment to prepare the unsaturated polyester resin, wherein the inorganic acid is one or a mixture of more than one of concentrated sulfuric acid, p-toluenesulfonic acid and trifluoromethanesulfonic acid.
More preferably, the reaction condition of the diol oligomer and the unsaturated carboxylic acid is 80-120 ℃.
Preferably, the cross-linking agent is hydrogen-containing silicone oil;
preferably low-viscosity hydrogen-containing silicone oil, and the chain length is 5-20.
Preferably, the silane coupling agent is one or a mixture of more than one of N-beta (aminoethyl) -gamma-aminopropylmethyldimethoxysilane (KH602) and 3-aminopropyltriethoxysilane (KH 550).
Preferably, the emulsifier is one or a mixture of more than one of nonylphenol polyoxyethylene ether (TX-10), fatty alcohol polyoxyethylene ether (AEO-3), sodium dodecyl benzene sulfonate, span series and tween series.
In the concrete low-viscosity modifier, the unsaturated polyester resin can improve the dispersing performance of high-grade concrete and improve the fluidity of the concrete, the coupling agent can reduce the surface tension of the concrete and further improve the fluidity of the concrete, the emulsion reaction can improve the stability of a system, and simultaneously the acid-base neutralization property of carbonate and the introduction of small bubbles improve the fluidity of the concrete.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the invention, the low-viscosity modifier is a low-viscosity modifier for high-grade concrete, is used for reducing the viscosity of the concrete when the high-grade concrete is mixed, and can be a finished product or prepared on site.
The preparation method specifically comprises the steps of carrying out hydrogenation reaction on unsaturated polyester resin to obtain saturated polyester resin, and then emulsifying and compounding the saturated polyester resin, a silane coupling agent and carbonate to obtain the low-viscosity modifier.
The low-viscosity modifier mainly comprises the following compounds:
in the structural formula, R1Is H or CH3M is 3 to 13, wherein R2Is H, CH3、COOH，R3Is COOH, COOCH3，n＝5～20。
In the examples, the unsaturated polyester resins used to make the low viscosity modifiers are either available as such or can be made by themselves. Wherein, the unsaturated polyester resin can be prepared by adopting dihydric alcohol oligomer and unsaturated carboxylic acid as raw materials.
Wherein the structure of the diol oligomer is as follows:
wherein R is1Is H or CH3When R is1When is H, m ═ 4 &13, such as m ═ 4, which is PEG200, m ═ 13, which is PEG 600; when R is1Is CH3When m is 5 to 20, for example, m is 3, which is PPG200, and m is 10, which is PPG 600.
Wherein the unsaturated carboxylic acid has the following structural formula:
wherein R is2Is H, CH3Or COOH, R3Is COOH or COOCH3(ii) a Such as when R2＝H，R3When COOH, the unsaturated carboxylic acid is acrylic acid; when R is2＝CH3，R3COOH, unsaturated carboxylic acid methacrylic acid; when R is2＝COOH，R3Unsaturated when COOH is fumaric acid; when R is2＝H，R3＝COOCH3When the unsaturated carboxylic acid is methyl acrylate; r2＝CH3，R3＝COOCH3When the unsaturated carboxylic acid is methyl methacrylate.
In the embodiment, the diol oligomer has better water solubility, and the generated unsaturated polyester resin also has better water solubility, so that the reaction can be smoothly carried out in an aqueous solution, and the diol can have higher conversion rate.
Meanwhile, in order to increase the conversion of the unsaturated carboxylic acid, the diol oligomer may be in an appropriate excess amount. In an embodiment, the ratio of the dihydric alcohol to the unsaturated carboxylic acid may be 2.5 to 8:1 by mass.
Further, in the examples, the method of preparing the unsaturated polyester resin from the diol oligomer and the unsaturated carboxylic acid is as follows: according to the amount of the substances, 40-60 parts of diol oligomer, 5-15 parts of unsaturated carboxylic acid and 1-5 parts of inorganic acid are put into a reaction vessel, and the mixture reacts for 3-5 hours at the temperature of 80-120 ℃ and is cooled to room temperature to obtain the unsaturated polyester resin.
In the embodiment, the raw material used in the hydrogenation reaction of the unsaturated polyester resin can be hydrogen-containing silicone oil, and further, low-viscosity hydrogen-containing silicone oil is preferred, and the chain length is 5-20.
In the embodiment, Karstedt's catalyst can be selected as the catalyst used in the hydrogenation reaction of the unsaturated polyester resin, and further, the catalyst is preferably a platinum-methyl vinyl siloxane complex.
In the embodiment, the silane coupling agent can be selected from one or more of N-beta (aminoethyl) -gamma-aminopropylmethyldimethoxysilane (KH602) and 3-aminopropyltriethoxysilane (KH 550).
In the embodiment, the emulsifier can be selected from one or more of nonylphenol polyoxyethylene ether (TX-10), fatty alcohol polyoxyethylene ether (AEO-3), sodium dodecylbenzene sulfonate, span series and Tween series.
In the examples, the carbonate may be selected from one or more of sodium carbonate, potassium carbonate, and sodium bicarbonate.
In the embodiment, when the low-viscosity modifier is prepared at present, the preparation method comprises the following steps:
adding 0.001-0.005 part of Karstedt catalyst and 5-15 parts of hydrogen-containing silicone oil into 5-10 parts of prepared unsaturated polyester resin by mass, and stirring at room temperature for 0.5 h; and adding 55-115 parts of water, 2-10 parts of silane coupling agent, 1-5 parts of emulsifier and 1-5 parts of carbonate, and quickly stirring for 1 hour to obtain uniformly dispersed white emulsion, namely the low-viscosity modifier.
Example 1
40 parts of (PEG 200), 5 parts of acrylic acid and 1 part of p-toluenesulfonic acid are added into a reaction kettle according to the mass parts of the substances, and the reaction is carried out for 3 hours at the temperature of 80 ℃ and cooled to room temperature to obtain transparent liquid with certain viscosity; adding 0.001 part of Karstedt catalyst and 5 parts of hydrogen-containing silicone oil, and stirring at room temperature for 0.5 h; 55 parts of water, 2 parts of a silane coupling agent (KH602), 1 part of an emulsifier (TX-10: AEO-3: 6: 4) and 1 part of sodium carbonate are added, and the mixture is rapidly stirred for 1 hour to obtain a uniformly dispersed white emulsion with the solid content of 50%.
Example 2
60 parts of (PEG 600), 10 parts of methacrylic acid and 3 parts of concentrated sulfuric acid are added into a reaction kettle according to the mass parts of the substances, and the mixture is reacted for 4 hours at the temperature of 100 ℃ and cooled to room temperature to obtain transparent liquid with certain viscosity; adding 0.003 part of Karstedt catalyst and 10 parts of hydrogen-containing silicone oil, and stirring for 0.5h at room temperature; adding 95 parts of water, 6 parts of silane coupling agent (KH550), 3 parts of emulsifier (sodium dodecyl benzene sulfonate) and 3 parts of sodium hydrocarbon, and quickly stirring for 1h to obtain uniformly dispersed white emulsion with the solid content of 50%.
Example 3
Adding 60 parts of PPG (PPG 600), 15 parts of maleic anhydride and 5 parts of trifluoromethanesulfonic acid into a reaction kettle in parts by mass of substances, reacting at 120 ℃ for 3 hours, and cooling to room temperature to obtain a transparent liquid with a certain viscosity; adding 0.003 part of Karstedt catalyst and 15 parts of hydrogen-containing silicone oil, and stirring at room temperature for 0.5 h; adding 115 parts of water, 10 parts of silane coupling agent (KH602), 5 parts of emulsifier (span 60: Tween 60: 1) and 5 parts of sodium bicarbonate, and rapidly stirring for 1h to obtain uniformly dispersed white emulsion with the solid content of 50%.
Example 4
50 parts of PPG (PPG 200), 10 parts of fumaric acid and 3 parts of p-toluenesulfonic acid are added into a reaction kettle in parts by mass of the substances, and the mixture is reacted for 5 hours at the temperature of 100 ℃ and cooled to room temperature to obtain transparent liquid with certain viscosity; adding 0.003 part of Karstedt catalyst and 10 parts of hydrogen-containing silicone oil, and stirring for 0.5h at room temperature; 85 parts of water, 6 parts of silane coupling agent (KH550), 3 parts of emulsifier (TX-10: AEO-3: 1) and 3 parts of potassium carbonate are added, and the mixture is rapidly stirred for 1 hour to obtain a white emulsion with the solid content of 50 percent and uniform dispersion.
Example 5
60 parts of (PEG 400), 15 parts of acrylic acid and 3 parts of concentrated sulfuric acid are added into a reaction kettle according to the mass parts of the substances, and the mixture is reacted for 3 hours at the temperature of 80 ℃ and cooled to room temperature to obtain transparent liquid with certain viscosity; adding 0.005 part of Karstedt catalyst and 15 parts of hydrogen-containing silicone oil, and stirring for 0.5h at room temperature; 113 parts of water, 10 parts of a silane coupling agent (KH 6020), 5 parts of an emulsifier (tween 60: span 80: 1), and 5 parts of sodium bicarbonate were added, and the mixture was rapidly stirred for 1 hour to obtain a uniformly dispersed white emulsion having a solid content of 50%.
Example 6
Putting 40 parts of PPG (PPG 400), 5 parts of fumaric acid and 1 part of concentrated sulfuric acid into a reaction kettle in parts by mass of substances, reacting for 4 hours at the temperature of 120 ℃, and cooling to room temperature to obtain transparent liquid with certain viscosity; adding 0.005 part of Karstedt catalyst and 5 parts of hydrogen-containing silicone oil, and stirring for 0.5h at room temperature; 63 parts of water, 6 parts of silane coupling agent (KH550), 3 parts of emulsifier (Tween 20: span 60: 1) and 3 parts of sodium carbonate are added, and the mixture is rapidly stirred for 1 hour to obtain a uniformly dispersed white emulsion with the solid content of 50%.
The experimental materials were as follows:
cement: red lion cement P.O 42.5.5; and (3) machining sand: local production in Guizhou, wherein the fineness modulus is 2.6-3.2; and (3) secondary crushed stone preparation: local production in Guizhou, 5-15 mm and 15-25 mm; water reducing agent: a standard high-performance water reducing agent HPWR-S sold by a company in Guizhou province has the solid content of 15 percent.
A sample which is not mixed with the low-viscosity concrete modifier is used as a blank sample, a viscosity reducer sold in Shanxi company is used as a comparison sample 1, a viscosity reducer sold in Jiangsu company is used as a comparison sample 2, and the commercially available viscosity reducer sample and the implementation examples 1, 2, 3, 4, 5 and 6 are uniformly prepared into a 15% solid content for concrete verification. C60 concrete performance tests are carried out according to GB 8076-2008 concrete admixture, and concrete tests are carried out on 4 samples of examples to compare the concrete flow performance and the compressive strength. The mixing ratio is shown in table 1:
TABLE 1 high-grade concrete experiment mixing proportion
According to the national standard GB/T50080-2016 standard for testing the performance of common concrete mixtures, the concrete viscosity test evaluation is carried out, and GB/T50081-2016 standard for testing the mechanical performance of common concrete tests is carried out on the table 1, and the measured data are shown in the table 2:
TABLE 2 concrete experiments
As can be seen from Table 2, the blank concrete not doped with the low-viscosity concrete modifier has an initial slump of 220mm, an expansion of 565mm, a rewinding time of 9.5s, a slump of 190mm after 2h, an expansion of 455mm, a rewinding time of 15.3s, and very viscous and poor flowing performance after 2 h; compared with a blank sample, the slump constant and the slump constant of the initial sample and the slump constant of the 2h are not greatly different, the initial rewinding time is relatively reduced by 3.3s, the rewinding time of the 2h is relatively reduced by 2.9s, the viscosity of the concrete is slightly improved, and the flowing property is general; compared with a blank sample, the slump and the expansion degree of the initial sample and the slump of the 2h sample are not greatly different, the initial rewinding time is relatively reduced by 3.5s, the rewinding time of the 2h sample is relatively reduced by 2.3s, the viscosity of the concrete is slightly improved, and the flowing property is general; compared with the blank samples, the slump and the expansion of the concrete are improved generally, and the initial and 2h cylinder-pouring time of the concrete is reduced obviously, wherein in the example 3, the initial slump is increased by 10mm relatively, the expansion is increased by 15mm relatively, the slump is increased by 5mm relatively after 2h, the expansion is increased by 10mm relatively, the flowing property of the concrete is good, the initial cylinder-pouring time is reduced by 5.2s relatively, the 2h cylinder-pouring time is reduced by 10.1s relatively, and the compressive strength of the concrete 3d, 7d and 28d is increased by 2.2MPa, 5.2MPa and 4.5MPa respectively.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A low viscosity modifier comprising a compound of the formula:
wherein R is1Is H or CH3M is 3 to 13, wherein R2Is H, CH3Or COOH, n is 5-20, and the low-viscosity modifier is prepared from unsaturated polyester resin, a silane coupling agent, an emulsifier and carbonate.
2. The low viscosity modifier according to claim 1, wherein the low viscosity modifier is prepared by a method comprising hydrogenating an unsaturated polyester resin to obtain a saturated polyester resin, and then reacting the obtained saturated polyester resin with a silane coupling agent, an emulsifier, and a carbonate to obtain a target compound.
3. The low viscosity modifier of claim 2, wherein the low viscosity modifier is prepared by a process further comprising reacting a diol oligomer with an unsaturated carboxylic acid in the presence of a mineral acid to form an unsaturated polyester resin.
4. The low viscosity modifier of claim 3, wherein the diol oligomer has the following structure:
wherein R1 is H or CH3，m＝3～13。
5. The low viscosity modifier of claim 3, wherein the unsaturated carboxylic acid has the formula:
wherein R is2Is H, CH3Or COOH, R3Is COOH or COOCH3。
6. The low viscosity modifier according to any one of claims 3 to 5, wherein the ratio of the diol oligomer to the unsaturated carboxylic acid is 2.5 to 8: 1.
7. The low viscosity modifier according to any one of claims 3 to 5, wherein the inorganic acid is selected from the group consisting of concentrated sulfuric acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, and mixtures thereof;
and under the environment of dihydric alcohol oligomer and unsaturated carboxylic acid inorganic acid, the reaction temperature is 80-120 ℃.
8. The low viscosity modifier according to claim 2, wherein the preparation method further comprises hydrogenation by reacting an unsaturated polyester resin with a low viscosity hydrogen-containing silicone oil, wherein the chain length of the low viscosity hydrogen-containing silicone oil is 5 to 20.
9. The low viscosity modifier according to claim 2, wherein the silane coupling agent is one or more of N- β (aminoethyl) - γ -aminopropylmethyldimethoxysilane and 3-aminopropyltriethoxysilane.
10. The low viscosity modifier according to claim 2, wherein the emulsifier is one or more selected from the group consisting of nonylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, sodium dodecylbenzenesulfonate, span series, and tween series.
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