CN104558434B - Siliceous polycarboxylate water-reducer, preparation method and the usage - Google Patents

Siliceous polycarboxylate water-reducer, preparation method and the usage Download PDF

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CN104558434B
CN104558434B CN201410782681.1A CN201410782681A CN104558434B CN 104558434 B CN104558434 B CN 104558434B CN 201410782681 A CN201410782681 A CN 201410782681A CN 104558434 B CN104558434 B CN 104558434B
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polycarboxylate water
reducer
siliceous
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water
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CN104558434A (en
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朱伟亮
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SHANGHAI TAIJIE CHEMICAL CO Ltd
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Abstract

The invention discloses a kind of siliceous polycarboxylate water-reducer, it is characterised in that molecular structural formula is shown in structural formula (IV):Wherein:A, b > 0, c >=0, d > 0;M1For organic silicon monomer structure, molecular structure is multiple silicone molecules being crosslinked by Si O Si keys;M2One of which for H or Na exists simultaneously;M3One of which for H or Na exists simultaneously;M4For one kind in ether type monomer.This patent introduces organosilicon structures in common polycarboxylate water-reducer structure.The double bond containing organic silicon monomer of macromolecular size is prepared by hydrolysis, the organic silicon monomer of preparation is used for polycarboxylate water-reducer synthetic system again, so that polycarboxylate water-reducer molecule size increases, it is allowed to be difficult into the intercalation configuration of soil, and then reaches anti-mud and slow down the effect of consumption.

Description

Siliceous polycarboxylate water-reducer, preparation method and the usage
Technical field
The present invention relates to a kind of siliceous polycarboxylate water-reducer, preparation method and the usage.
Background technology
Polycarboxylate water-reducer is also known as super plasticizer (Polycarboxylate Superplasticizer), is a kind of common Building auxiliary agent, particularly in high-grade concrete, concrete prefabricated element, high-rise pumping architectural engineering, polycarboxylic acids diminishing Agent turns into one of concrete admixture essential at present.Polycarboxylate water-reducer is earliest by Japanese Kao company in 20th century Invent the eighties and apply for a patent, by the development in more than ten years, just largely substitute traditional naphthalene system in Japan and American-European countries and subtract Aqua and lignin water reducer.The article for the relevant polycarboxylate water-reducer performance that Japanese scholars in 1985 are delivered is relevant earliest The document of polycarboxylate water-reducer synthetic method, the document, which have studied carboxylic serials reactive polymer, to be used to control slump Loss.Japan starts to promote polycarboxylate water-reducer in 1990s.The research of initial polycarboxylate water-reducer is mainly esters Monomer is as reaction raw materials, and such polycarboxylate water-reducer is usually two-step method synthesis, first by with reactivity double bond Esterification occurs for carboxylic acid and polyethylene glycol, synthesizes double bond containing esters polyalkylene glycol monomer, then by it with double bond containing carboxylic acid, The raw materials such as sulfonic compound carry out Raolical polymerizable.According to the literature, after nineteen ninety-five, in Japanese polycarboxylate water-reducer Consumption alreadys exceed naphthalene water reducer consumption.As polycarboxylate water-reducer is constantly expanded using scope, consumption constantly increases, its phase Close research and be increasingly becoming focus.After 2000, ether type monomer technology of the synthesis with double bond is gradually ripe, and occurs in that one-step method Synthesize the document report of polycarboxylic acids.
The research of domestic polycarboxylate water-reducer is started late, and product category is relatively single, and performance and Foreign Advanced Lerel are still There is certain gap, but also there are numerous academy's successes to emerge in large numbers in recent years.Professor Li Chongzhi of Tsing-Hua University is first with polyethylene glycol, horse Carry out acid anhydrides for raw material, be determined by esterification synthesizing polyethylene glycol maleate monomer, and to its performance;Jiangsu is built Absorption dispersive property of the graduate Ran Qian equalitys according to water reducer is built, main chain has been synthesized simultaneous with anion and cation PACP water reducers;Qiu Xueqing of South China Science & Engineering University etc. think the shorter polycarboxylate water-reducer dispersive property of polyethylene oxide side chains compared with Difference is that polyethylene oxide side chains are longer, may be such that side chain is mutually wound because steric hindrance acts on smaller, hinders water reducer Molecular structure is unfolded in the solution.
The country still has a great deal of architectural engineering using the water reducer of non-polycarboxylic acid at present, though these conventional water reducing agents So by compounding can improving performance within the specific limits, but the need for can not meeting high-grade concrete.And it is more and more Architectural engineering high requirement can be proposed to polycarboxylate water-reducer initial performance and time dependent simultaneously, in current Practical Project It is difficult to solve often through preparation method.In addition, China has turned into, polycarboxylate water-reducer usage amount is maximum and yield increase is most fast Area, this is primarily due to Foreign Architecture theory and gradually abandons high-rise building, thus to high-performance polycarboxylic acids water reducing agent demand Amount has been cut down;The country is in the fast-developing construction period, and a large amount of landmarks put into operation in succession, thus to high-performance And the demand of the polycarboxylate water-reducer of property constantly increases, but the husky resource of domestic architecture of high quality is increasingly not enough, numerous Area uses the higher river sand and Shan Sha of clay content, thus will be further obvious for the demand of anti-chamotte mould polycarboxylate water-reducer.
Polycarboxylate water-reducer due to its preferably initial water-reducing rate, good slow setting function of slump protection, advantages of environment protection, It is used widely in world wide, but its pectinate texture, in the higher system of clay content, performance is often poor, or need big Amplitude increases its volume, causes cost to increase.For mechanism of the polycarboxylate water-reducer intolerant to mud and clay, proposed in previous literature A variety of hypothesis.Wherein research of professor J.Plank to polycarboxylate water-reducer adsorption process thinks exist in mud class and clay big Intercalation and space are measured, causes the polycarboxylate water-reducer molecule of pectinate texture to be consumed by intercalation and gap absorption, so as to reduce The utilization rate and dispersiveness of polycarboxylate water-reducer molecule.
The content of the invention
One of purpose of the present invention is that there is provided a kind of siliceous polycarboxylic acids diminishing in order to overcome deficiency of the prior art Agent.
To realize object above, the present invention is achieved through the following technical solutions:
A kind of siliceous polycarboxylate water-reducer, it is characterised in that molecular structural formula is shown in structural formula (IV):
Wherein:
A, b > 0, c >=0, d > 0;
M1For organic silicon monomer structure, molecular structure is multiple silicone molecules being crosslinked by Si-O-Si keys;
M2One of which for-H or-Na exists simultaneously;
M3One of which for-H or-Na exists simultaneously;
M4For one kind in ether type monomer.
Preferably, it is characterised in that the M1For organic silicon monomer, contain amino.
Preferably, the M1 structural formulas are (II) or (III):
Preferably, each repeat unit is block distributed in structural formula (IV).
Another object of the present invention is that there is provided a kind of siliceous polycarboxylate water-reducer in order to overcome deficiency of the prior art Preparation method.
To realize object above, the present invention is achieved through the following technical solutions:
The preparation method of siliceous polycarboxylate water-reducer, it is characterised in that (1), by silane and acid anhydrides containing amino containing There is reaction generation organic silicon monomer under the alkalescence condition of water;(2), by the reaction product of step (1), side chain monomer and carboxylic acid in mistake Sulfuric acid compound triggers lower polymerisation.
Preferably, the silane containing amino is aminopropyltriethoxywerene werene (KH-550) or aminopropyl three Methoxy silane (APS).
Preferably, the ether type monomer is modified polyether or acrylic polyethylene glycol;The esters monomer is poly- second two The acrylate or methacrylate of alcohol monomethyl ether.
Preferably, the carboxylic acid is acrylic acid, methacrylic acid, maleic anhydride or itaconic acid.
Preferably, in the step (1), silane and anhydride reaction of the part containing amino are made first, then in potassium hydroxide Ethanol or methanol solution catalysis under, add after water, then silane reaction of the another part containing amino be added dropwise.
Preferably, the silane containing amino and anhydride molar ratio are 1:1.2~1:1.5;Mole of ethanol is added after reaction Number is 0.5 times~1 times of the molal quantity of the acid anhydrides of initial reaction;The molal quantity for adding water is 1.5 times~5 of the silane containing amino Times;KOH ethanol solution concentration is 0.1-0.4mol/L.
Preferably, the molal quantity of the silane containing amino of dropwise addition reacts with maleic anhydride for the initial silane containing amino and produced 5~15 times of both thing molal quantity sums.
Preferably, the reaction temperature of the step (2) is 50 DEG C -80 DEG C.
Preferably, in the step (2), the chain-transferring agent aqueous solution is added also into reactant.
Preferably, the chain-transferring agent is TGA, mercaptopropionic acid, methylpropene sodium sulfonate or sodium allylsulfonate.
Preferably, in the step (2), the ratio of each raw material is:
The ratio that organic silicon monomer molal quantity accounts for total moles monomer is 0.2~0.5;
The ratio that ether type monomer molal quantity accounts for total moles monomer is 0.5~0.8;
The ratio of carboxylic acid molal quantity and total monomer molal quantity is 2.0~5.5;
Over cure acids initiator amount is the 0.3%~2.0% of reactant gross mass;
Chain-transferring agent consumption is the 0.05%~1.0% of reactant gross mass.
Preferably, in the step (2), it is additionally added the sulfonate containing double bond.
Preferably, the sulfonate containing double bond is selected from sodium allylsulfonate, methylpropene sodium sulfonate or 2- acrylamides -2- Methyl propane sulfonic acid.
Preferably, after the completion of step (2) reaction, then it is 6-8 that reactant is neutralized into pH value, and adjustment solid content is extremely 20%-40%.
Another object of the present invention is that there is provided a kind of siliceous polycarboxylate water-reducer in order to overcome deficiency of the prior art Purposes.
To realize object above, the present invention is achieved through the following technical solutions:
Foregoing siliceous polycarboxylate water-reducer is used in cement.
This patent introduces organosilicon structures in common polycarboxylate water-reducer structure.Macromolecular is prepared by hydrolysis The double bond containing organic silicon monomer of size, then the organic silicon monomer of preparation is used for polycarboxylate water-reducer synthetic system, so that Polycarboxylate water-reducer molecule size increases, and is allowed to be difficult into the intercalation configuration of soil, and then reach anti-mud and slow down consumption Effect.
Brief description of the drawings
Fig. 1 is common polycarboxylate water-reducer infrared spectrogram.
Fig. 2 is siliceous polycarboxylate water-reducer infrared spectrogram.
Embodiment
The preparation method for illustrating the anti-chamotte mould polycarboxylate water-reducer of organosilicon provided by the present invention comprises the following steps:
1) macromolecular size organic silicon monomer is synthesized:
Organosilicon radical is introduced in polymer architecture, organosilicon materials molecular structure used is as schemed shown in (I), to introduce activity The silicone molecules structure of double bond adds the unsaturated monomer knot prepared after organosilicon materials hydrolysis as schemed shown in (II), further Structure is as schemed shown in (III);
Shown in the siliceous polycarboxylate water-reducer such as structural formula (IV) prepared:
This step is that maleic anhydride of the silane coupler aminopropyltriethoxywerene werene (KH-550) with drying is being cooled down Under the conditions of chemically react, C=C double bond structures are introduced in KH-550 molecules by amido link;Again at potassium hydroxide (KOH) Ethanol solution catalysis under, add suitable quantity of water and KH-550, make the ethoxy based structures of silane coupler first hydrolyze after dehydrated crosslinking, Form the silicone molecules of multiple macromolecular sizes being crosslinked by Si-O-Si structures.
This step preparation method describes in detail as follows:
The dry maleic anhydride solid of certain metering is added in reaction vessel, under the conditions of water cooling condition or ice salt bath, Dried silane resin acceptor kh-550 (technical grade) is at the uniform velocity added dropwise, and reaction system is made by magnetic stirring apparatus quick rotation The rapid loss of heat that is uniform and producing reaction, after after completion of dropwise addition, continuing reaction for a period of time, in question response device no longer Produce and stop reaction after heat.To react unreacted maleic anhydride, consumption is complete, adds appropriate water and potassium hydroxide (KOH) ethanol solution, mixes slowly and a certain amount of silane resin acceptor kh-550 is slowly added dropwise, react at room temperature, KH-550 drop Dosage determines the size of the molecular weight, i.e. molecular dimension of the organosilicon structures ultimately produced.After reaction terminates, vacuum distillation is removed The second alcohol and water of residual, obtains the organic silicon monomer structure with Raolical polymerizable activity.
Its reaction raw materials ratio is:KH-550 is 1 with maleic anhydride mol ratio:1.2~1:1.5;Ethanol is added after reaction Molal quantity is 0.5 times~1 times of the molal quantity of the maleic anhydride of initial reaction;The molal quantity for adding water is 1.5 times of KH-550 ~5 times;KOH ethanol solution concentration is 0.2mol/L.The KH-550 of dropwise addition molal quantity is initial KH-550 and maleic anhydride 5~15 times of reaction product molal quantity, the KH-550 molal quantitys of dropwise addition are more, point of final macromolecular size organic silicon monomer Son amount is bigger.
2) synthesis of the polycarboxylate water-reducer containing organosilicon.This step radical polymerization step reaction temperature at 50~80 DEG C, Hydrogen peroxide can be decomposed rapidly in this temperature so as to produce free radical, therefore present invention initiator used is persulfate Class, can be one or more of mixing in sodium peroxydisulfate, potassium peroxydisulfate or ammonium persulfate etc., can also add appropriate reproducibility Material increase initiator produces free radical ability.
This step describes in detail as follows:In reaction vessel according to metered proportions add step 1) prepare organosilicon list Body, polyether monomer TPEG and sulfonate (such as sodium allylsulfonate, methylpropene sodium sulfonate, 2- acrylamide -2- first containing double bond Base propane sulfonic acid etc.), distilled water is added, the mechanical agitation under 50~80 DEG C of reaction temperatures is added after over cure acids initiator, constant speed Unsaturated carboxylic acid solution (acrylic acid, methacrylic acid, maleic anhydride etc.) and the chain-transferring agent aqueous solution (TGA or mercapto is added dropwise Base propionic acid), time for adding control continues to react to stop reaction after 1~2h after 120~240min, completion of dropping, obtains copolymerization Product;
Polymerisation material rate is:The ratio that organic silicon monomer molal quantity accounts for total moles monomer is 0.2~0.5;Ether The ratio that class monomer molar number accounts for total moles monomer is 0.5~0.8;The ratio of carboxylic acid molal quantity and total monomer molal quantity is 2.0~5.5;Over cure acids initiator amount is the 0.3%~2.0% of reactant gross mass;Sulfydryl class chain-transferring agent consumption is The 0.05%~1.0% of reactant gross mass.
3) post processing is neutralized:By step 2) prepared by siliceous polycarboxylic acid polymer add aqueous slkali to be neutralized to 6~8, adjustment Solid content obtains the polycarboxylate water-reducer containing macromolecule organosilicon radical to 20%~40%.
When the present invention uses unsaturated sulfonic acid salt as reaction raw materials, because its own has certain chain-transferring agent to act on, because And can suitably reduce sulfydryl class chain tra nsfer and consumption.
The present invention is further described with reference to embodiments.
Embodiment 1:
The maleic anhydride that 200g is dried is added in three-necked flask, slowly 250g is at the uniform velocity added under ice salt bath cooling condition Silane resin acceptor kh-550, and quickly stir, stirring reaction 1h.Under rapid mixing conditions, it is 0.2mol/ to add 25ml concentration L KOH ethanol solution, adds 70g water after stirring, at the uniform velocity add 1000gKH-550, adds time 5h.Stirring at low speed Under the conditions of react 12h, vacuum distillation removes residual moisture and alcohol compound, obtains the larger silicon-containing monomer of molecular weight.
The above-mentioned modified polyether (TPEG) for preparing silicon-containing monomer 100g and 150g molecular weight 2400 is added into reaction vessel, plus Enter 200g distilled water, stirring is warming up to 65~80 DEG C, add initiator sodium peroxydisulfate 3.0g, it is to be mixed it is uniform after start dropwise addition third Continue to react after the 5wt% solution 40g of olefin(e) acid 55.0g and chain-transferring agent TGA, time for adding 120min, completion of dropping 90min.PH value is adjusted to 6~7 with 30% sodium hydroxide solution, is diluted with water to 40%, as siliceous anti-chamotte mould polycarboxylic acids Water reducer.
Embodiment 2:
The maleic anhydride that 200g is dried is added in three-necked flask, slowly 250g is at the uniform velocity added under ice salt bath cooling condition Silane resin acceptor kh-550, and quickly stir, stirring reaction 1h.Under rapid mixing conditions, it is 0.2mol/ to add 20ml concentration L KOH ethanol solution, adds 70g water after stirring, at the uniform velocity add 500gKH-550, adds time 3h.Stirring at low speed Under the conditions of react 6h, vacuum distillation removes residual moisture and alcohol compound, obtains the less silicon-containing monomer of molecular weight.
The above-mentioned modified polyether (TPEG) for preparing silicon-containing monomer 100g and 200g molecular weight 2400 is added into reaction vessel, plus Enter 200g distilled water, stirring is warming up to 65~80 DEG C, add initiator sodium peroxydisulfate 3.0g, it is to be mixed it is uniform after start dropwise addition third Continue to react after the 5wt% solution 35g of olefin(e) acid 50.0g and chain-transferring agent TGA, time for adding 120min, completion of dropping 90min.PH value is adjusted to 6~7 with 30% sodium hydroxide solution, is diluted with water to 40%, as siliceous anti-chamotte mould polycarboxylic acids Water reducer.
Embodiment 3:
The maleic anhydride that 200g is dried is added in three-necked flask, slowly 250g is at the uniform velocity added under ice salt bath cooling condition Silane resin acceptor kh-550, and quickly stir, stirring reaction 1h.Under rapid mixing conditions, it is 0.2mol/ to add 25ml concentration L KOH ethanol solution, adds 70g water after stirring, at the uniform velocity add 1000gKH-550, adds time 5h.Stirring at low speed Under the conditions of react 12h, vacuum distillation removes residual moisture and alcohol compound, obtains the larger silicon-containing monomer of molecular weight.
The above-mentioned modified polyether (TPEG) for preparing silicon-containing monomer 150g and 100g molecular weight 1200 is added into reaction vessel, plus Enter 200g distilled water, stirring is warming up to 65~80 DEG C, add initiator sodium peroxydisulfate 5.0g, it is to be mixed it is uniform after start dropwise addition third Continue to react after the 5wt% solution 40g of olefin(e) acid 65.0g and chain-transferring agent TGA, time for adding 180min, completion of dropping 60min.PH value is adjusted to 6~7 with 30% sodium hydroxide solution, is diluted with water to 40%, as siliceous anti-chamotte mould polycarboxylic acids Water reducer.
Embodiment 4:
The maleic anhydride that 200g is dried is added in three-necked flask, slowly 250g is at the uniform velocity added under ice salt bath cooling condition Silane resin acceptor kh-550, and quickly stir, stirring reaction 1h.Under rapid mixing conditions, it is 0.2mol/ to add 25ml concentration L KOH ethanol solution, adds 70g water after stirring, at the uniform velocity add 1000gKH-550, adds time 5h.Stirring at low speed Under the conditions of react 12h, vacuum distillation removes residual moisture and alcohol compound, obtains silicon-containing monomer.
The above-mentioned acrylic polyethylene glycol (HPEG) for preparing silicon-containing monomer 100g and 150g molecular weight 2400 is added into reaction Container, adds 200g distilled water, and stirring is warming up to 70~85 DEG C, adds initiator ammonium persulfate 5.0g, it is to be mixed it is uniform after open The 5wt% solution 40g of acrylic acid 60.0g and chain-transferring agent TGA are added dropwise in beginning, and time for adding 120min, completion of dropping is follow-up Continuous reaction 90min.PH value is adjusted to 6~7 with 30% sodium hydroxide solution, is diluted with water to 40%, as siliceous anti-chamotte mould Polycarboxylate water-reducer.
Embodiment 5:
The maleic anhydride that 200g is dried is added in three-necked flask, slowly 250g is at the uniform velocity added under ice salt bath cooling condition Silane resin acceptor kh-550, and quickly stir, stirring reaction 1h.Under rapid mixing conditions, it is 0.2mol/ to add 25ml concentration L KOH ethanol solution, adds 70g water after stirring, at the uniform velocity add 500gKH-550, adds time 3h.Stirring at low speed Under the conditions of react 6h, vacuum distillation removes residual moisture and alcohol compound, obtains the less silicon-containing monomer of molecular weight.
The above-mentioned modified polyether (TPEG) for preparing silicon-containing monomer 100g and 100g molecular weight 2400 is added into reaction vessel, plus Enter 200g distilled water and 6g methylpropene sodium sulfonates (MAS), stirring is warming up to 65~80 DEG C, adds initiator sodium peroxydisulfate 5.0g, it is to be mixed it is uniform after start that the 5wt% solution 20g of acrylic acid 60.0g and chain-transferring agent TGA, time for adding is added dropwise Continue to react 60min after 180min, completion of dropping.PH value is adjusted to 6~7 with 30% sodium hydroxide solution, is diluted with water to 40%, as siliceous anti-chamotte mould polycarboxylate water-reducer.
The specific embodiment of the present invention is described in detail above, but it is intended only as example, and the present invention is not limited It is formed on particular embodiments described above.To those skilled in the art, it is any to the equivalent modifications that carry out of the present invention and Substitute also all among scope of the invention.Therefore, the impartial conversion made without departing from the spirit and scope of the invention and Modification, all should be contained within the scope of the invention.
Embodiment 6:
The maleic anhydride that 200g is dried is added in three-necked flask, slowly 250g is at the uniform velocity added under ice salt bath cooling condition Silane resin acceptor kh-550, and quickly stir, stirring reaction 1h.Under rapid mixing conditions, it is 0.2mol/ to add 25ml concentration L KOH ethanol solution, adds 70g water after stirring, at the uniform velocity add 800gKH-550, adds time 4h.Stirring at low speed Under the conditions of react 9h, vacuum distillation removes residual moisture and alcohol compound, obtains the moderate silicon-containing monomer of molecular weight.
By the above-mentioned acrylic acid for preparing silicon-containing monomer 100g and the poly glycol monomethyl ether (APEG) of 150g molecular weight 2400 Ester adds reaction vessel, adds 200g distilled water and 5g methylpropene sodium sulfonates (MAS), and stirring is warming up to 65~80 DEG C, addition Initiator sodium peroxydisulfate 5.0g, it is to be mixed it is uniform after start that acrylic acid 60.0g is added dropwise and the 5wt% of chain-transferring agent TGA is molten Continue to react 60min after liquid 20g, time for adding 150min, completion of dropping.PH value is adjusted to 6 with 30% sodium hydroxide solution ~7,40% is diluted with water to, as siliceous anti-chamotte mould polycarboxylate water-reducer.
Embodiment 7
The maleic anhydride that 200g is dried is added in three-necked flask, slowly 220g is at the uniform velocity added under ice salt bath cooling condition Silane coupler TSL 8330 (APS), and quickly stir, stirring reaction 1h.Under rapid mixing conditions, plus Enter the ethanol solution that 25ml concentration is 0.2mol/L KOH, 70g water is added after stirring, 800gAPS is at the uniform velocity added, add Time 4h.9h is reacted under the conditions of stirring at low speed, vacuum distillation removes residual moisture and alcohol compound, obtains molecular weight moderate Silicon-containing monomer.
By the above-mentioned acrylic acid for preparing silicon-containing monomer 100g and the poly glycol monomethyl ether (APEG) of 150g molecular weight 2400 Ester adds reaction vessel, adds 200g distilled water and 5g methylpropene sodium sulfonates (MAS), and stirring is warming up to 65~80 DEG C, addition Initiator sodium peroxydisulfate 5.0g, it is to be mixed it is uniform after start that acrylic acid 60.0g is added dropwise and the 5wt% of chain-transferring agent TGA is molten Continue to react 60min after liquid 20g, time for adding 150min, completion of dropping.PH value is adjusted to 6 with 30% sodium hydroxide solution ~7,40% is diluted with water to, as siliceous anti-chamotte mould polycarboxylate water-reducer.
The beneficial effects of the invention are as follows:
1. the present invention is prepared for a kind of organic silicon monomer of macromolecule;
2. the present invention is using macromolecule organic silicon monomer and modified polyether TPEG as raw material, and with polymerization activity Carboxyl acid copolymer, is prepared for a kind of polycarboxylate water-reducer of anti-mud absorption;
3. the present invention is characterized to the siliceous water reducer of preparation, and is compared with common polycarboxylate water-reducer, with true The fixed effect whether there is preferably anti-mud to adsorb.
The siliceous polycarboxylate water-reducer of preparation is tested respectively and commonly using TPEG as the polycarboxylate water-reducer of Material synthesis Pulp flowage and its through when mobility.Experiment cement used is the ordinary portland cement of Shanghai conch 42.5, with reference to GB/8076- 2008 test pulp flowages, fluidity extension diameter.
Unit is millimeter (mm), and experimental result is as follows:
Initially 30min 60min 90min 120min 180min
Siliceous polycarboxylate water-reducer (example 1) 292 286 278 265 249 237
Siliceous polycarboxylate water-reducer (example 4) 298 291 285 273 259 245
Ether type monomer water reducer (I) 288 280 273 258 240 218
Ether type monomer water reducer (II) 295 286 275 253 233 212
Building sand is rinsed and removes soil, dries and removes moisture, then mixes 5% and 10% soil group wherein respectively Point, it is well mixed, its divergence of the husky measuring of progress glue.
(containing mud 5%)
Initially 30min 60min 90min 120min
Siliceous polycarboxylate water-reducer (example 1) 245 230 202 189 165
Ether type monomer water reducer (I) 250 226 181 160 120
(containing mud 10%)
Initially 30min 60min 90min 120min
Siliceous polycarboxylate water-reducer (example 1) 248 225 195 177 148
Ether type monomer water reducer (I) 243 217 170 145 ——
Proved by pulp flowage test result, under the conditions of identical volume, add macromolecule organic silicon monomer The slump retaining of polycarboxylate water-reducer cement paste is better than general T PEG class polycarboxylate water-reducers.In glue sand experiment, contain mud in height Under the conditions of, the polycarboxylate water-reducer containing macromolecule organosilicon through when divergence be substantially better than common polycarboxylate water-reducer, This is primarily due to soil specific surface area greatly, particularly the intercalation configuration in soil, and general T PEG class polycarboxylate water-reducers are shorter Largely consumed in time.On the one hand, the organosilicon radical of macromolecule has certain electric charge, with earth surfaces formation electrostatic Repulsion is acted on, and on the other hand the effect of its steric hindrance is bigger, the polycarboxylate water-reducer molecule of tree is not easily accessible soil Intercalation configuration in, so as to avoid diminishing agent molecule from quickly being consumed, enhance cement paste and the husky system of glue through when keep Performance.
The siliceous polycarboxylate water-reducer of test is determined by Fourier formula infrared spectrum (IR), it was demonstrated that silicone molecules are existing Effect is grafted in polycarboxylate water-reducer molecule.Fig. 1 is the infrared spectrum for the common polycarboxylate water-reducer for being not introduced into organosilicon structures Figure.Fig. 2 is the infrared spectrogram of siliceous polycarboxylate water-reducer prepared by above example.Wherein, 1100cm-1Neighbouring strong absorption Peak is the characteristic absorption peak of C-O-C functional groups, 1080cm-1Neighbouring strong absworption peak is Si-O-Si characteristic absorption peak;770cm-1Neighbouring middle strong absworption peak is the NH of primary amide base2The characteristic absorption peak of outer surface movement, 1400cm-1Neighbouring middle strong absworption peak For the absworption peak of N-H stretching vibrations.Results of IR proved by introducing unsaturated double-bond in silicone molecules, then Raolical polymerizable system is used it for, effectively organosilicon structures can be introduced into polycarboxylate water-reducer molecule, so that Prepare siliceous polycarboxylate water-reducer.
Compound mensuration is carried out to siliceous polycarboxylate water-reducer by high performance liquid chromatography (HPLC), acrylic acid remaining ratio is 0.86%;TPEG remaining ratios are 2.13%;Organic silicon monomer remaining ratio is 1.85%.Various reaction raw materials pass through polymerization Reaction generation polycarboxylate water-reducer molecule.
After testing, remaining embodiment can reach and embodiment 1,4 identical effects.
This patent introduces organosilicon structures in common polycarboxylate water-reducer structure.Macromolecular is prepared by hydrolysis The double bond containing organic silicon monomer of size, then the organic silicon monomer of preparation is used for polycarboxylate water-reducer synthetic system, so that Polycarboxylate water-reducer molecule size increases, and is allowed to be difficult into the intercalation configuration of soil, and then reach anti-mud and slow down consumption Effect.
Embodiment in the present invention is only used for that the present invention will be described, and is not construed as limiting the scope of claims limitation, Other substantial equivalent replacements that those skilled in that art are contemplated that, all fall in the scope of protection of the present invention.

Claims (12)

1. a kind of siliceous polycarboxylate water-reducer, it is characterised in that molecular structural formula is shown in structural formula (IV):
Wherein:
A, b > 0, c >=0, d > 0;
M1For organic silicon monomer structure, molecular structure is
M2One of which for-H or-Na exists simultaneously;
M3One of which for-H or-Na exists simultaneously;
M4For one kind in ether type monomer.
2. siliceous polycarboxylate water-reducer according to claim 1, it is characterised in that each repeat unit is in structural formula (IV) Block distributed.
3. the preparation method of the siliceous polycarboxylate water-reducer described in claim 1 or 2, it is characterised in that (1), amino will be contained Silane and maleic anhydride react under the alkalescence condition containing water and generates organic silicon monomer;(2), the reaction of step (1) is produced Thing, ether type monomer and the acrylic acid polymerisation under the initiation of over cure acid compounds.
4. the preparation method of siliceous polycarboxylate water-reducer according to claim 3, it is characterised in that described containing amino Silane is aminopropyltriethoxywerene werene or TSL 8330.
5. the preparation method of siliceous polycarboxylate water-reducer according to claim 3, it is characterised in that in the step (1), Silane of the part containing amino is reacted with maleic anhydride first, then under ethanol or the methanol solution catalysis of potassium hydroxide, add After water, then silane reaction of the another part containing amino is added dropwise.
6. the preparation method of siliceous polycarboxylate water-reducer according to claim 3, it is characterised in that the step (2) Reaction temperature is 50 DEG C -80 DEG C.
7. the preparation method of siliceous polycarboxylate water-reducer according to claim 3, it is characterised in that in the step (2), The chain-transferring agent aqueous solution is added also into reactant.
8. the preparation method of siliceous polycarboxylate water-reducer according to claim 7, it is characterised in that the chain-transferring agent is TGA, mercaptopropionic acid, methylpropene sodium sulfonate or sodium allylsulfonate.
9. the preparation method of siliceous polycarboxylate water-reducer according to claim 7, it is characterised in that in the step (2), The ratio of each raw material is:
Over cure acids initiator amount is the 0.3%~2.0% of reactant gross mass;
Chain-transferring agent consumption is the 0.05%~1.0% of reactant gross mass.
10. the preparation method of siliceous polycarboxylate water-reducer according to claim 3, it is characterised in that the step (2) In, it is additionally added the sulfonate containing double bond;Sulfonate containing double bond is sodium allylsulfonate.
11. the preparation method of siliceous polycarboxylate water-reducer according to claim 3, it is characterised in that step (2) has been reacted Cheng Hou, then reactant is neutralized to pH value for 6-8, adjustment solid content to 20%-40%.
12. the siliceous polycarboxylate water-reducer described in claim 1 or 2 is used in cement.
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