CN102532433B - Allyl polyether maleic acid (anhydride) copolymer, preparation and application thereof - Google Patents
Allyl polyether maleic acid (anhydride) copolymer, preparation and application thereof Download PDFInfo
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Abstract
The invention relates to an allyl polyether maleic acid (anhydride) copolymer and a preparation thereof, which can effectively improve the conversion rates of allyl polyether and maleic acid (anhydride). The invention also provides an application of the allyl polyether maleic acid (anhydride) copolymer as a water reducer. The preparation method of the allyl polyether maleic acid (anhydride) copolymer is polymerization of a monomer A and a monomer B in an aqueous solution, wherein the molar ratio of the monomer A and the monomer B is 1:1 to 1:9, the monomer A is shown in general formula (I), the monomer B is shown in general formula (II) or (III); all the monomer A and B are added into a reaction container once; the mixture is stirred uniformly; a redox system initiator is firstly added for reaction; then a persulfate initiator is added for reaction till the conversion rate of the allyl polyether is 85-95% and the conversion rate of the maleic acid (anhydride) and its salts is 75-90%; the weight average molecular weight of the copolymer is 40,000-100,000.
Description
Technical field
The present invention relates to a kind of allyl polyether base toxilic acid (acid anhydride) based copolymer, its preparation method and application.
Background technology
Water reducer, be called again dispersion agent or fluidizer, and Main Function has: (1) is keeping, under the condition that concrete component is constant, improving its workability; (2) under given workability condition, reduce mixing water content, to improve concrete strength, improve weather resistance; (3), under the condition that does not change the military service performance, reduce unit cement consumption, with the problems such as thermal stresses that minimizing is crept, contraction and hydration heat of cement cause.
In recent years, the develop rapidly of domestic construction industry makes the demand of water reducer increase year by year.Yet, although the condensation polymer type water reducers such as tradition naphthalene system, melamine series have good dispersiveness, the fresh concrete mobility through the time loss large, and to have adopted naphthalene, formaldehyde and the vitriol oil during production be starting material, unfriendly to environment, a lot of engineering restriction application.In the situation that overcome above-mentioned defect, polycarboxylic acids dehydragent not only water-reducing rate is high, good to cement adaptability, and synthesis technique relatively simple, produce pollution-freely, therefore in a lot of important engineerings, be applied.
At present, domestic polycarboxylic acids dehydragent mainly contains two kinds: (1) polyester water reducer, water reducer prepared as large monomer by methoxyl group polyethers list (methyl) acrylate that methoxyl group polyethers and (methyl) vinylformic acid generates of usining; (2) polyethers water reducer, using alkenyl polyether or its modified product as the main water reducer that greatly prepared by monomer.Compare the polyester water reducer, the polyethers water reducer has the advantages such as synthesis technique is simple, cost is low, polymerization concentration is high, product stock good stability.Therefore the polyethers water reducer is used in domestic most of producer favor, but the synthetic technology of China's polyethers water reducer immature also is in Rapid development stage.
The variety of raw material that the polyethers water reducer is used is more.The large monomer of unsaturated polyether mainly contains vinyl polyether, allyl polyether and butenyl polyethers, and their derivative; Minor comonomer mainly contains (methyl) vinylformic acid, toxilic acid (acid anhydride) and other functional minor comonomer.The activity of above-mentioned various monomers differs larger, when carrying out copolymerization, how to make copolymerization efficiently preferably between monomer, forms desirable comb copolymer water reducer, needs suitable polymerization environment.
Japan catalyst company is studied early aspect the polyethers water reducer, at its patent CN1148329, CN1821149, detailed introduction is arranged in CN1303875, but the large monomer used for methylallyl polyethers (initiator is methallyl alcohol) and first for butenyl polyethers (initiator is 3-methyl-3-propylene-1-alcohol), these two kinds of unsaturated polyether prices are more expensive, and domestic apparent availability is limited, acrylic acid price is also more expensive simultaneously, and the expensive chain-transfer agent that used in production process that the smell is awful, make final cost higher.
In order to reduce the cost of water reducer product, investigators expect allyl polyether naturally, because its price is low, the starting material source is abundant.On the other hand, toxilic acid (acid anhydride) and salt thereof are suitable with the allyl polyether reactivity ratio, and price is starkly lower than (methyl) vinylformic acid, and when the industrial chemicals price volalility is larger, the advantage that this cost is low is more obvious.Except cost is low, allyl polyether base toxilic acid (acid anhydride) based water reducer also possesses that synthesis technique is simple, production technique environmental protection, polymerization concentration advantages of higher.But under general polymerization environment, the polymerization activity of allyl polyether and toxilic acid (acid anhydride) and salt thereof is all poor, is difficult to obtain desirable polyalcohol water reducing agent.For example, at patent CN1756724, CN1768015, all introduced in CN101786824 that to take methacrylic polyethers and allyl polyether be large monomer, toxilic acid (acid anhydride) is main minor comonomer, synthetic water reducer has the high dispersive ability and prevents the ability of slump-loss, but needs higher volume to realize same performance while finding take allyl polyether as large monomer.
Patent CN101225148, CN101786824, CN101386490, CN101186460 all relates to take allyl polyether and toxilic acid (acid anhydride) and salt thereof the method as the synthetic water reducer of monomer.At the bottom of introduction is put into still by allyl polyether monomer and toxilic acid (acid anhydride) monomer, by dripping other functional monomers, (during difference, use) and make water reducer under the effect of persulphate or redox system initiator, this method utilizes the alternating copolymerization of functional monomer and toxilic acid (acid anhydride) to improve the transformation efficiency of monomer, but be limited by the polymerization activity of allyl polyether self, the transformation efficiency of large monomer is still lower, and diminishing and function of slump protection are restricted.This kind is by adding the 3rd monomer or adding the common method that more monomer improves allyl polyether and toxilic acid (acid anhydride) transformation efficiency, the applicant has also carried out a large amount of experiments, can only partly solve the shortcoming that the allyl polyether monomer reactivity is lower, the amplitude improved is very limited, and the general easy homopolymerization of the functional monomer added, and expensive, increased cost, produce the complicacy that has also increased equipment simultaneously.Therefore when take allyl polyether and toxilic acid (acid anhydride) when monomer prepares water reducer, the raising monomer conversion will be the most important thing.
Summary of the invention
The invention provides the preparation method of a kind of allyl polyether base toxilic acid (acid anhydride) based copolymer, can effectively improve the transformation efficiency of allyl polyether and toxilic acid (acid anhydride).
The present invention also provides allyl polyether base toxilic acid (acid anhydride) based copolymer of above-mentioned preparation method's gained.
The present invention also provides the application of described allyl polyether base toxilic acid (acid anhydride) based copolymer as water reducer.
Applicant of the present invention finds through a large amount of experimental studies, adopts two initiator systems (water soluble oxidized reduction system initiator and inorganic peroxysulfate system initiator) can significantly improve the transformation efficiency of monomer in the aqueous solution polymerization system of allyl polyether and toxilic acid (acid anhydride) and salt thereof.Generally in the aqueous solution polymerization system of allyl polyether and toxilic acid (acid anhydride) and salt thereof, use single initiator system of the prior art (for example: redox system initiator, inorganic peroxysulfate initiator, azo-initiator or other class initiator), the allyl polyether transformation efficiency is 60～75%, toxilic acid (acid anhydride) and salt transformation efficiency thereof are 55～70%, use of the present invention pair of initiator system, the allyl polyether transformation efficiency is 85～95%, and toxilic acid (acid anhydride) and salt transformation efficiency thereof are 75～90%.As everyone knows, improve the transformation efficiency of monomer, can avoid raw-material waste, improve the effective concentration of water reducer, performance also significantly promotes, and is a kind of more cost effective method, the products molecule design and construction simultaneously obtained more approaching, be conducive to its optimization of synthesis.When the applicant studies the single-initiator system, by adopting stage by stage, cause, high low-temp reaction, extend the reaction times, increases the approach such as amount of initiator, is used alone or as a mixture these approach, can only improve on a small quantity monomer conversion.But the discovery that the applicant is surprised adopts two initiator systems can significantly improve the transformation efficiency of monomer.
The preparation method of described a kind of allyl polyether base toxilic acid (acid anhydride) based copolymer, be polymerized in the aqueous solution by monomer A and monomers B, and the mol ratio of monomer A and monomers B is 1: 1 to 1: 9, wherein:
General formula for monomer A (I) means:
Wherein: M
1a kind of in hydrogen atom, potassium ion, sodium ion, ammonium radical ion;-R
1o-means ethylene oxide unit, the natural number that m is 8～135;-R
2o-means propylene oxide unit, the integer that n is 0～10,
General formula for monomers B (II) or (III) expression:
Wherein: M
2and M
3can be identical or different, be hydrogen atom independently of one another, the monovalence metal, divalent metal, ammonium root or organic ammonium, while preparing described allyl polyether base toxilic acid (acid anhydride) based water reducer, by whole monomer A with B is disposable adds in reaction vessel, after stirring, first adding redox system initiator for reaction to allyl polyether transformation efficiency is 60～75%, toxilic acid (acid anhydride) and salt transformation efficiency thereof are 55～70%, and then add persulfate initiator react to the allyl polyether transformation efficiency be 85～95%, toxilic acid (acid anhydride) and salt transformation efficiency thereof are 75～90%, the weight-average molecular weight of described allyl polyether base toxilic acid (acid anhydride) based copolymer is 40, 000～100, 000.Add the redox system initiator for reaction, this stage has the transformation efficiency reached in ordinary method, but only adopt this initiator system, all be difficult to further improve transformation efficiency by increasing amount of initiator or time expand, yet but can significantly improve transformation efficiency in conjunction with follow-up persulfate initiator, final allyl polyether transformation efficiency is 85～95%, and toxilic acid (acid anhydride) and salt transformation efficiency thereof are 75～90%.The weight-average molecular weight of described allyl polyether base toxilic acid (acid anhydride) based copolymer more preferably 55,000～85,000.Monomer conversion of the present invention records by the integral area conversion of GPC, and the integral area of hypothesis allyl polyether, polymkeric substance and maleic anhydride equates than coefficient with its quality, in the measuring method of this transformation efficiency document below, report (Qiao Min is arranged, Ran Qianping, Zhou Dongliang etc. the impact [J] of the molecular structure information of polycarboxylate water-reducer on its dispersing property. green building, 2011,5:63-65.).
Monomers B is selected at least one in toxilic acid (acid anhydride) and salt thereof, preferably usings maleic anhydride as neccessary composition.The increase of main chain carboxyl-content is conducive to improve the water-reducing rate of water reducer, but carboxyl can cause when too high concrete slump loss to accelerate.The mol ratio of monomer A and monomers B is preferably 2: 3 to 1: 3.
Comonomer A molecular weight is about 400～6000 within the scope of the present invention, and preferred molecular weight is about 1200～3000.When monomer A is allyl polyethenoxy ether, m=8～135, preferably m=26～67; When selecting block polyether, polyoxypropylene segment and polyoxyethylene segment mol ratio n/m≤1/5, preferably n/m≤1/10, can regulate concrete air content by the propylene oxide segment, improves the adaptability to cement.Monomer A can a kind of molecular weight, also can various molecular weights mix in any proportion.Along with the side chain lengths of water reducer molecule increases, concrete cohesiveness increases, and slump retention improves, but chain length can weaken its water-reducing rate because of the corresponding reduction of the content of other functional group while surpassing certain value.
Preferably, adding the temperature of redox system reaction is 35～55 ℃, and adding the temperature of persulfate initiator reaction is 80～95 ℃.
Preferably, in described redox system initiator, the mole number of oxygenant accounts for 0.5～20% of monomer A and B total mole number, and the mole number of reductive agent is 10～100% of oxygenant mole number.Further preferably, in described redox system initiator, the mole number of oxygenant accounts for 2～6% of monomer A and B total mole number, and the mole number of reductive agent is 20～40% of oxygenant mole number.Redox system initiator used in the present invention, wherein oxygenant partly comprises water miscible superoxide and persulphate, preferably hydrogen peroxide.The reductive agent part is restriction especially not, can use conventional reductive agent.As: low valence metal ion Fe
2+salt, rongalite (rongalite), alkali metal sulfite, L-AA (salt) etc.The preferably combination of hydrogen peroxide and L-AA.When the oxygenant consumption surpasses 20%, the polymerization degree of the multipolymer that the first step causes reduces, and the backbone molecule amount is too low; When consumption, lower than 0.5% the time, the initiation reaction effect is poor, neither be preferred.The mode that adds of hydrogen peroxide is when system temperature arrives 35～45 ℃, disposable adding.When the reductive agent consumption lower than the oxygenant mole number 10% the time, it is limited that the first step causes role, a large amount of monomers can not be activated.On the other hand, when the reductive agent consumption surpass the oxygenant mole number 100% the time, after the first step initiation reaction finishes, residual a large amount of reductive agent in system, cause the effect of follow-up persulfate initiator to reduce.The mode that adds of L-AA is within 10～30 minutes after hydrogen peroxide adds system, to adopt the mode dripped continuously again.
The present invention's persulfate initiator system used comprises: ammonium persulphate, Potassium Persulphate, Sodium Persulfate etc., initiator system of ammonium persulfate.Its consumption is 0.5～10% of comonomer total mole number, preferably 1～5%.The persulfate initiator consumption is lower than 0.5%, can not make the residual monomer effecting reaction after the first step causes, and higher than 10% the time, can cause on the one hand cost to increase, and in follow-up neutralization reaction, has on the other hand the ammonia of a large amount of irritating smells to emit.The mode that adds of persulfate initiator is, after the redox system initiator for reaction finishes, to start continuous dropping when temperature is risen to 80～95 ℃.
Preferably, the total initial weight concentration of monomer A and monomers B is 30%～70%.
Without adding chain-transfer agent, save cost on the one hand in water reducer preparation process of the present invention, avoided on the other hand the irritating smell of product, more environmental protection.The adjustment of the molecular weight mainly amount by above-mentioned initiator and polymerization concentration, polymerization temperature is regulated.
Polyreaction is cooled to 40～50 ℃ after finishing, and directly adds mineral alkali to carry out neutralization reaction, is preferably sodium hydroxide, potassium hydroxide, ammonium hydroxide.Adding the consumption of mineral alkali to take the pH value of conditioned reaction product is advisable as 6.5～8.The pH value is too high or too low, and the package stability of multipolymer is all bad.
The weight-average molecular weight of cement dispersants multipolymer of the present invention is controlled at 40,000～100, and 000, more preferably be controlled at 55,000～85,000, if molecular weight is too large or too little, all can weaken the dispersion effect to cement.
Cement dispersants of the present invention conventional volume in use is 0.05%～0.3% of total gelling material weight.If volume, can not be satisfactory to the dispersion effect of cement lower than 0.05%; If volume higher than 0.3%, causes waste economically, and dispersion effect does not further increase.
The advantage that is better than single initiator system of prior art below the two initiator systems of use in the present invention can obtain: (1) has significantly improved the transformation efficiency of allyl polyether and toxilic acid (acid anhydride) and salt thereof, make take allyl polyether and toxilic acid (acid anhydride) and salt thereof as the method for the synthetic ethers polycarboxylic acid water reducing agent of main raw material(s) more competitive, that the excellent water reducer (2) of a kind of cost lower performance is when keeping the good conversion rate, molecular structure can be prepared reasonable, be easy to control molecular weight and distribution thereof, (3) can easily adjust the ratio of polyether lateral chain and adsorption group, (4) can under higher polymerization concentration, carry out, problem simultaneously that not there will be water reducer low temperature crystallization.
While adopting the method for water-soluble radical copolymerization to carry out the preparation of system water reducer of the present invention, owing to being limited by the low problem of the polymerization activity of starting material own, adopt conventional polymerization process (single-initiator system) to have the low defect of the described monomer conversion of background technology.The applicant, through lot of experiments, obtains the polymerization process that of the present invention pair of initiator system causes step by step, has obviously improved the transformation efficiency of monomer.Resulting allyl polyether base toxilic acid (acid anhydride) based copolymer as water reducer have that volume is low, dispersion and retentivity is good, water-reducing rate is high, adaptable advantage, can not only in large-scale, emphasis, highly difficult engineering, use, and the commercial market that can be applied to rise gradually in recent years.
The accompanying drawing explanation
The GPC elution curve that Fig. 1 is allyl polyether base toxilic acid (acid anhydride) based copolymer, wherein scheme the GPC elution curve that a, b, c, d are respectively PC3, CT1, CT2, CT3.
Embodiment
Following examples have described in more detail the process that the method according to this invention prepares allyl polyether base toxilic acid (acid anhydride) based water reducer, and these embodiment provide in the mode of explanation, its purpose is to allow the person skilled in the art can understand content of the present invention and implement according to this, but these embodiment never limit the scope of the invention.All equivalences that spirit is done according to the present invention change or modify, within all should being encompassed in protection scope of the present invention.
In the embodiment of the present invention and comparative example, all water reducer molecular weight and monomer conversion are used aqueous gel permeation chromatography (GPC) to be measured.Experiment condition is as follows:
Gel column: Shodex SB806+803 two root chromatogram column series connection
Eluant: 0.1M NaNO
3solution
Moving phase speed: 1.0ml/min
Injection: 20 μ l 0.5% aqueous solution
Detector: Shodex RI-71 type differential refraction detector
Standard substance: polyoxyethylene glycol GPC standard specimen (Sigma-Aldrich, molecular weight 1010000,478000,263000,118000,44700,18600,6690,1960,628,232)
In Application Example of the present invention, except special instruction, the cement adopted is little wild field 52.5R.P.II cement, the medium sand that sand is fineness modulus Mx=2.6, and stone is the rubble that particle diameter is 5～20mm continuous grading.The flowing degree of net paste of cement test is carried out with reference to the GB/T8077-2000 standard, and amount of water is 87g, stirs after 3 minutes and measure flowing degree of net paste of cement on sheet glass.The slump and slump-loss are carried out with reference to JC473-2001 " concrete pump-feed agent " relevant regulations.Water-reducing rate, air content test method are carried out with reference to the relevant regulations of GB8076-97 " concrete admixture "
Use the listed main raw material(s) code name of table 1 in embodiment and comparative example:
Table 1 synthesis example and comparative example main raw material(s) code name
Embodiment and comparative example
The monomer that embodiment and comparative example adopt and ratio, initiator system and mole dosage, weight concentration, monomer conversion and molecular weight are listed table 2 in.
[embodiment mono-]
Add 250g deionized water, 60g A-1 (0.15mol), 360g A-3 (0.15mol) and 58.8g B-1 (0.6mol) in the glass reactor that thermometer, agitator, dropping funnel, reflux condensing tube and nitrogen conduit are housed, stir rising temperature for dissolving, and use the nitrogen purging reaction vessel, be warming up to 35 ℃ and keep constant temperature after, add 4.08g30%P-H (0.036mol) and 0.025g P-F.The homogeneous aqueous solution of first 70g being contained to 1.58g P-L (0.009mol), add in reactor in the mode at the uniform velocity dripped, and time for adding is 1h; Then system temperature is risen to 80 ℃, more at the uniform velocity drip the initiator solution that 133g contains 6.15g P-A (0.027mol), time for adding is 4h.Complete soln dropwises follow-up continuation of insurance temperature 2h, is cooled to 50 ℃, adds sodium hydroxide to be neutralized to pH=7, obtains the light yellow transparent liquid that solid content is 50.7%, and weight-average molecular weight is 58000, is follow-up test called after PC1.
[embodiment bis-]
Add 250g deionized water, 288g A-2 (0.24mol) and 17.52g B-1 (0.24mol) in the glass reactor that thermometer, agitator, dropping funnel, reflux condensing tube and nitrogen conduit are housed, stir rising temperature for dissolving, and use the nitrogen purging reaction vessel, be warming up to 35 ℃ and keep constant temperature after, add 2.18g30%P-H (0.019mol).The homogeneous aqueous solution of first 70g being contained to 0.85g P-L (0.0048mol), add in reactor in the mode at the uniform velocity dripped, and time for adding is 1h; Then system temperature is risen to 80 ℃, more at the uniform velocity drip the initiator solution that 133g contains 3.28g P-A (0.014mol), time for adding is 4h.Complete soln dropwises follow-up continuation of insurance temperature 2h, is cooled to 50 ℃, adds sodium hydroxide to be neutralized to pH=7, obtains the light yellow transparent liquid that solid content is 40.2%, and weight-average molecular weight is 61000, is follow-up test called after PC2.
[embodiment tri-]
Add 140g deionized water, 480g A-3 (0.2mol) and 58.8g B-1 (0.6mol) in the glass reactor that thermometer, agitator, dropping funnel, reflux condensing tube and nitrogen conduit are housed, stir rising temperature for dissolving, and use the nitrogen purging reaction vessel, be warming up to 35 ℃ and keep constant temperature after, add 3.63g30%P-H (0.032mol).The homogeneous aqueous solution of first 70g being contained to 1.41g P-L (0.008mol), add in reactor in the mode at the uniform velocity dripped, and time for adding is 1h; Then system temperature is risen to 80 ℃, more at the uniform velocity drip the initiator solution that 133g contains 5.47g P-A (0.024mol), time for adding is 4h.Complete soln dropwises follow-up continuation of insurance temperature 2h, is cooled to 50 ℃, adds sodium hydroxide to be neutralized to pH=7, obtains the light yellow transparent liquid that solid content is 60.4%, and weight-average molecular weight is 68000, is follow-up test called after PC3.
[embodiment tetra-]
Add 150g deionized water, 480g A-4 (0.16mol) and 62.72g B-1 (0.64mol) in the glass reactor that thermometer, agitator, dropping funnel, reflux condensing tube and nitrogen conduit are housed, stir rising temperature for dissolving, and use the nitrogen purging reaction vessel, be warming up to 35 ℃ and keep constant temperature after, add 3.63g30%P-H (0.032mol).The homogeneous aqueous solution of first 70g being contained to 1.41g P-L (0.008mol), add in reactor in the mode at the uniform velocity dripped, and time for adding is 1h; Then system temperature is risen to 80 ℃, more at the uniform velocity drip the initiator solution that 133g contains 5.47g P-A (0.024mol), time for adding is 2h.Complete soln dropwises follow-up continuation of insurance temperature 2h, is cooled to 50 ℃, adds sodium hydroxide to be neutralized to pH=7, obtains the light yellow transparent liquid that solid content is 59.6%, and weight-average molecular weight is 76000, is follow-up test called after PC4.
[embodiment five]
Add 100g deionized water, 360g A-5 (0.06mol) and 52.92g B-1 (0.54mol) in the glass reactor that thermometer, agitator, dropping funnel, reflux condensing tube and nitrogen conduit are housed, stir rising temperature for dissolving, and use the nitrogen purging reaction vessel, be warming up to 35 ℃ and keep constant temperature after, add 2.72g30%P-H (0.024mol).The homogeneous aqueous solution of first 30g being contained to 1.06g P-L (0.006mol), add in reactor in the mode at the uniform velocity dripped, and time for adding is 1h; Then system temperature is risen to 80 ℃, more at the uniform velocity drip the initiator solution that 80g contains 4.1g P-A (0.018mol), time for adding is 2h.Complete soln dropwises follow-up continuation of insurance temperature 2h, is cooled to 50 ℃, adds sodium hydroxide to be neutralized to pH=7, obtains the light yellow transparent liquid that solid content is 69.8%, and weight-average molecular weight is 81000, is follow-up test called after PC5.
[embodiment six]
Add 145g deionized water, 480g A-3 (0.2mol) and 58g B-2 (0.5mol) in the glass reactor that thermometer, agitator, dropping funnel, reflux condensing tube and nitrogen conduit are housed, stir rising temperature for dissolving, and use the nitrogen purging reaction vessel, be warming up to 45 ℃ and keep constant temperature after, add 6.66g30%P-N (0.028mol).The homogeneous aqueous solution of first 70g being contained to 2.91g P-S (0.028mol), add in reactor in the mode at the uniform velocity dripped, and time for adding is 1h; Then system temperature is risen to 90 ℃, more at the uniform velocity drip the initiator solution that 133g contains 9.45g P-K (0.035mol), time for adding is 4h.Complete soln dropwises follow-up continuation of insurance temperature 2h, is cooled to 50 ℃, adds sodium hydroxide to be neutralized to pH=7, obtains the light yellow transparent liquid that solid content is 59.8%, and weight-average molecular weight is 65000, is follow-up test called after PC6.
[embodiment seven]
Add 135g deionized water, 480g A-3 (0.2mol) and 46.4g B-2 (0.4mol) in the glass reactor that thermometer, agitator, dropping funnel, reflux condensing tube and nitrogen conduit are housed, stir rising temperature for dissolving, and use the nitrogen purging reaction vessel, be warming up to 45 ℃ and keep constant temperature after, add 8.57g30%P-N (0.036mol).The homogeneous aqueous solution of first 70g being contained to 2.5g P-S (0.028mol), add in reactor in the mode at the uniform velocity dripped, and time for adding is 1h; Then system temperature is risen to 90 ℃, more at the uniform velocity drip the initiator solution that 133g contains 1.43g P-N (0.006mol), time for adding is 4h.Complete soln dropwises follow-up continuation of insurance temperature 2h, is cooled to 50 ℃, adds sodium hydroxide to be neutralized to pH=7, obtains the light yellow transparent liquid that solid content is 59.9%, and weight-average molecular weight is 59000, is follow-up test called after PC7.
[embodiment eight]
Add 165g deionized water, 480g A-3 (0.2mol) and 92.8g B-2 (0.8mol) in the glass reactor that thermometer, agitator, dropping funnel, reflux condensing tube and nitrogen conduit are housed, stir rising temperature for dissolving, and use the nitrogen purging reaction vessel, be warming up to 45 ℃ and keep constant temperature after, add 2.27g30%P-H (0.02mol).The homogeneous aqueous solution of first 70g being contained to 0.59g P-D (0.005mol), add in reactor in the mode at the uniform velocity dripped, and time for adding is 1h; Then system temperature is risen to 90 ℃, more at the uniform velocity drip the initiator solution that 133g contains 11.4gP-A (0.05mol), time for adding is 4h.Complete soln dropwises follow-up continuation of insurance temperature 2h, is cooled to 50 ℃, adds sodium hydroxide to be neutralized to pH=7, obtains the light yellow transparent liquid that solid content is 59.5%, and weight-average molecular weight is 72000, is follow-up test called after PC8.
[embodiment nine]
Add 170g deionized water, 480g A-6 (0.2mol) and 96g B-3 (0.6mol) in the glass reactor that thermometer, agitator, dropping funnel, reflux condensing tube and nitrogen conduit are housed, stir rising temperature for dissolving, and use the nitrogen purging reaction vessel, be warming up to 35 ℃ and keep constant temperature after, add 3.63g30%P-H (0.032mol).The homogeneous aqueous solution of first 70g being contained to 1.42g P-D (0.012mol), add in reactor in the mode at the uniform velocity dripped, and time for adding is 1h; Then system temperature is risen to 80 ℃, more at the uniform velocity drip the initiator solution that 133g contains 1.82g P-A (0.008mol), time for adding is 4h.Complete soln dropwises follow-up continuation of insurance temperature 2h, is cooled to 50 ℃, adds sodium hydroxide to be neutralized to pH=7, obtains the light yellow transparent liquid that solid content is 59.3%, and weight-average molecular weight is 68000, is follow-up test called after PC9.
[embodiment ten]
Add 170g deionized water, 480g A-7 (0.2mol) and 96g B-3 (0.6mol) in the glass reactor that thermometer, agitator, dropping funnel, reflux condensing tube and nitrogen conduit are housed, stir rising temperature for dissolving, and use the nitrogen purging reaction vessel, be warming up to 35 ℃ and keep constant temperature after, add 3.63g30%P-H (0.032mol).The homogeneous aqueous solution of first 70g being contained to 0.94g P-D (0.008mol), add in reactor in the mode at the uniform velocity dripped, and time for adding is 1h; Then system temperature is risen to 80 ℃, more at the uniform velocity drip the initiator solution that 133g contains 5.47g P-A (0.024mol), time for adding is 4h.Complete soln dropwises follow-up continuation of insurance temperature 2h, is cooled to 50 ℃, adds sodium hydroxide to be neutralized to pH=7, obtains the light yellow transparent liquid that solid content is 60.2%, and weight-average molecular weight is 69000, is follow-up test called after PC10.
[comparative example one]
Add 273g deionized water, 480g A-3 (0.2mol) and 58.8g B-1 (0.6mol) in the glass reactor that thermometer, agitator, dropping funnel, reflux condensing tube and nitrogen conduit are housed, stir rising temperature for dissolving, and use the nitrogen purging reaction vessel, be warming up to 35 ℃ and keep constant temperature after, add 7.25g30%P-H (0.064mol).Then the homogeneous aqueous solution of 70g being contained to 2.82g P-L (0.016mol), add in reactor in the mode at the uniform velocity dripped, and time for adding is 1h.Complete soln dropwises follow-up continuation of insurance temperature 2h, adds sodium hydroxide to be neutralized to pH=7, obtains the light yellow transparent liquid that solid content is 59.8%, and weight-average molecular weight is 28000, is follow-up test called after CT1.
[comparative example two]
Add 210g deionized water, 480g A-3 (0.2mol) and 58.84g B-1 (0.6mol) in the glass reactor that thermometer, agitator, dropping funnel, reflux condensing tube and nitrogen conduit are housed, stir rising temperature for dissolving, and use the nitrogen purging reaction vessel, be warming up to 90 ℃ and keep constant temperature, then the homogeneous aqueous solution of 133g being contained to 10.94g P-A (0.048mol), in the mode at the uniform velocity dripped, add in reactor, time for adding is 4h.Complete soln dropwises follow-up continuation of insurance temperature 2h, is cooled to 50 ℃, adds sodium hydroxide to be neutralized to pH=7, obtains the light yellow transparent liquid that solid content is 60.2%, and weight-average molecular weight is 29000, is follow-up test called after CT2.
[comparative example three]
Add 125.8g deionized water, 410g A-3 (0.1708mol) and 41.4g B-2 (0.0.3570mol) in the glass reactor that thermometer, agitator, dropping funnel, reflux condensing tube and nitrogen conduit are housed, stir rising temperature for dissolving, and use the nitrogen purging reaction vessel, be warming up to 65 ℃.Keeping the temperature in container is 65 ℃, adds wherein the aqueous solution be comprised of 1.453g P-H and 27.61g deionized water.Then, dripped and dissolve the aqueous solution prepared by 1.882g P-L in the 35.76g deionized water to reactor with 1 hour.Then keep temperature to be 65 ℃ within 1 hour, finishing polyreactions after this.Then be cooled to 50 ℃, add sodium hydroxide to be neutralized to pH=7, obtain the light yellow transparent liquid that solid content is 70.0%, weight-average molecular weight is 32000, is follow-up test called after CT3.
Table 2 water reducer synthesis condition and monomer conversion and molecular weight
Annotate: in embodiment 1, monomer A is mixed by A-1 and A-3 at 1: 1, and the mole number of monomer A is A-1 and A-3 mole number sum.Comparative example 3 is prepared by the method for introducing according to patent CN1768015.
Below by corresponding experiment, by above-described embodiment and comparative example, obtaining water reducer, contrasted, advantage of the present invention is further elaborated.
(1) GPC test experiments
The GPC testing experiment is molecular weight and the monomer conversion in order to measure serial water reducer sample, is that synthetic method is the most directly estimated, and advantage of the present invention can better be described.The water reducer sample, after the efficient gel chromatographic column is separated, detects through differential refraction detector, obtains the GPC elution curve, and as shown in Figure 1, embodiment only be take the PC3 elution curve as representative, and other embodiment spectrogram similarly, does not add and repeats.In Fig. 1, C
1peak represents high-molecular weight polymer, C
2peak represents medium molecule weight polymers, C
3peak represents low-molecular weight polymer, and the A peak represents the large monomer of allyl polyether, and the B peak represents toxilic acid (acid anhydride) and salt thereof.When spectrogram is processed, use the Origin data processing software to carry out swarming, the product weight-average molecular weight can directly be obtained by the Origin data processing software.While calculating monomer conversion, adopt peak area method.If the integral area at polymkeric substance peak is C (peak C
1, C
2c
3the integral area sum), the integral area of allyl polyether is A, toxilic acid (acid anhydride) and salt integral area thereof are B, when water reducer is synthetic, the quality that feeds intake of the large monomer of polyethers accounts for the feed intake percentage ratio of quality of raw material and is designated as f, in order to simplify calculating, the total mass that guarantees the reaction after product is still M, control is aggregated in (or taking other measures that component can not volatilized) under air-proof condition and carries out (certainly, under air-proof condition, do not carry out can obtaining polymkeric substance of the present invention yet, only otherwise can make solvent too volatilize, affect polymerization and get final product).The quality that can calculate the large monomer of the rear residue of reaction according to the GPC curve of product is:
(r
1, r
2, r
3for the integral area that is respectively allyl polyether, polymkeric substance and maleic anhydride with its quality than coefficient, suppose that herein the three equates, has approximately fallen when calculating transformation efficiency).The transformation efficiency X of allyl polyether
acan mean with formula IV, in like manner can obtain the transformation efficiency of toxilic acid (acid anhydride) and salt thereof.
Molecular weight of product and monomer conversion that all embodiment and comparative example obtain see the above table 2.By Fig. 1 and table 2, can be found out, adopt the of the present invention couple of preparation method that initiator system causes stage by stage, the water reducer molecular weight obtained is higher, and the transformation efficiency of allyl polyether and toxilic acid (acid anhydride) and salt thereof is apparently higher than the water reducer that adopts single initiator system to make in comparative example.
(2) clean slurry experiment
For dispersing property and the dispersion retention of estimating prepared allyl polyether base toxilic acid (acid anhydride) based water reducer of the present invention, carried out the flowing degree of net paste of cement test with reference to the GB/T8077-2000 standard, cement 300g, amount of water is 87g, stir and measure flowing degree of net paste of cement after 3 minutes on sheet glass, and test the clean slurry degree of mobilization after 1 hour, experimental result is in Table 3.
Table 3 flowing degree of net paste of cement
By contrast PC3 and CT1, CT2, visible in the situation that reach identical clean slurry initial flow degree, the volume of the PC3 that adopts dual initiator system of the present invention to prepare reduces by 35% than the volume of CT1 that routinely prepared by the single-initiator method and CT2, and PC3 has degree of mobilization retention preferably, and CT1 and CT2 just started to descend after 1 hour.By contrast PC7 and CT3, worked as monomer and ratio homogeneous phase at that time as seen, the CT3 that adopts patent CN1768015 method to prepare, under the condition of identical volume, only starch degree of mobilization and hold facility thereof and be starkly lower than the PC7 prepared by the inventive method.By the above-mentioned performance data explanation of prepared water reducer to other embodiment that when has neither part nor lot in contrast, allyl polyether base toxilic acid (acid anhydride) based water reducer that the present invention adopts dual initiator system to prepare can be than obtaining cement dispersing property preferably under low-dosage, and have and disperse preferably retention, and ordinary method causes the obviously deteriorated of performance because monomer conversion is low.
(3) concrete experiments
It is representative that the synthetic PC3 of embodiment 3 is selected in this test, investigate dispersing property and the slump hold facility of water reducer, test fixedly water reducer solid volume is cement weight 0.2%, it is 21 ± 1cm that the adjustment water consumption makes fresh concrete just make the slump, and water-reducing rate, air content test method are carried out with reference to the relevant regulations of GB8076-97 " concrete admixture ".Test-results is in Table 4.
The impact of table 4 allyl polyether base of the present invention toxilic acid (being) water reducer on concrete performance
Test-results shows: allyl polyether base toxilic acid (acid anhydride) the based water reducer PC3 prepared according to the method for the invention has higher water-reducing rate, at the solid volume, be cement weight 0.2% the time, water-reducing rate is up to 31.4%, and controlling under the approaching condition of air content, the water reducer water-reducing rate prepared according to ordinary method only has 21% left and right, and the water reducer CT3 water-reducing rate that adopts patent CN1768015 method to prepare also only has 22.5%.And while adding PC3 of the present invention, fresh concrete 1h slump-loss is very little.
Claims (15)
1. the preparation method of an allyl polyether base toxilic acid (acid anhydride) based copolymer, is characterized in that, by monomer A and monomers B, in the aqueous solution, is polymerized, and the mol ratio of monomer A and monomers B is 1:1 to 1:9, wherein:
Monomer A means with logical formula I:
Monomers B means with logical formula II or (III):
wherein: M
2and M
3can be identical or different, be hydrogen atom independently of one another, the monovalence metal, divalent metal, ammonium root or organic ammonium, while preparing described allyl polyether base toxilic acid (acid anhydride) based copolymer, by whole monomer A with B is disposable adds in reaction vessel, after stirring, first adding redox system initiator for reaction to allyl polyether transformation efficiency is 60～75%, toxilic acid (acid anhydride) and salt transformation efficiency thereof are 55～70%, and then add persulfate initiator react to the allyl polyether transformation efficiency be 85～95%, toxilic acid (acid anhydride) and salt transformation efficiency thereof are 75～90%, the weight-average molecular weight of described allyl polyether base toxilic acid (acid anhydride) based copolymer is 40, 000～100, 000.
2. the preparation method of allyl polyether base toxilic acid as claimed in claim 1 (acid anhydride) based copolymer, it is characterized in that, in described redox system initiator, the mole number of oxygenant accounts for 0.5～20% of monomer A and B total mole number, and the mole number of reductive agent is 10～100% of oxygenant mole number.
3. the preparation method of allyl polyether base toxilic acid as claimed in claim 2 (acid anhydride) based copolymer, it is characterized in that, in described redox system initiator, the mole number of oxygenant accounts for 2～6% of monomer A and B total mole number, and the mole number of reductive agent is 20～40% of oxygenant mole number.
4. the preparation method of allyl polyether base toxilic acid (acid anhydride) based copolymer as claimed in claim 2 or claim 3, is characterized in that, described oxygenant is hydrogen peroxide.
5. the preparation method of allyl polyether base toxilic acid as claimed in claim 4 (acid anhydride) based copolymer, is characterized in that, described reductive agent is L-AA.
6. the preparation method of allyl polyether base toxilic acid as claimed in claim 4 (acid anhydride) based copolymer, it is characterized in that, hydrogen peroxide is disposable to add, within 10～30 minutes after hydrogen peroxide adds polymerization system, adopt the mode dripped continuously to add L-AA, persulfate initiator adopts continuous dropping mode to add again.
7. the preparation method of allyl polyether base toxilic acid (acid anhydride) based copolymer as claimed in claim 2 or claim 3, it is characterized in that, the temperature that adds the redox system initiator for reaction is 35～55 ℃, reaction times is 1～2 hour, adding the temperature of persulfate initiator reaction is 80～95 ℃, and the reaction times is 2～6 hours.
8. the preparation method of allyl polyether base toxilic acid (acid anhydride) based copolymer as claimed any one in claims 1 to 3, is characterized in that, the mol ratio of monomer A and monomers B is 2:3 to 1:3.
9. as the preparation method of the described allyl polyether base of any one in claim 1-3 toxilic acid (acid anhydride) based copolymer, it is characterized in that, the total initial weight concentration of monomer A and monomers B is 30%～70%.
10. as the preparation method of the described allyl polyether base of any one in claim 1-3 toxilic acid (acid anhydride) based copolymer, it is characterized in that, the weight-average molecular weight of described allyl polyether base toxilic acid (acid anhydride) based copolymer is 55,000～85,000.
11. the preparation method as the described allyl polyether base of any one in claim 1-3 toxilic acid (acid anhydride) based copolymer, is characterized in that, n/m≤1/5.
12. the preparation method of allyl polyether base toxilic acid as claimed in claim 11 (acid anhydride) based copolymer, is characterized in that n/m≤1/10.
13. the preparation method as the described allyl polyether base of any one in claim 1-3 toxilic acid (acid anhydride) based copolymer, is characterized in that, n=0, m=26～67.
14. allyl polyether base toxilic acid (acid anhydride) based copolymer that in claim 1-12, the described preparation method of any one obtains.
15. the described allyl polyether base of claim 14 toxilic acid (acid anhydride) based copolymer is as the application of water reducer.
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| CN101225148A (en) * | 2007-12-21 | 2008-07-23 | 北京工业大学 | Method for synthesizing allyl polyether-type high-performance water reducing agent |
| CN101538134A (en) * | 2009-04-14 | 2009-09-23 | 大连市建筑科学研究设计院股份有限公司 | Polyether class polycarboxylic acid high-efficiency water reducing agent and preparation method thereof |
| CN101974135A (en) * | 2010-10-15 | 2011-02-16 | 北京工业大学 | Normal-temperature synthesis method for polycarboxylic acid water-reducing agent |
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| CN101225148A (en) * | 2007-12-21 | 2008-07-23 | 北京工业大学 | Method for synthesizing allyl polyether-type high-performance water reducing agent |
| CN101538134A (en) * | 2009-04-14 | 2009-09-23 | 大连市建筑科学研究设计院股份有限公司 | Polyether class polycarboxylic acid high-efficiency water reducing agent and preparation method thereof |
| CN101974135A (en) * | 2010-10-15 | 2011-02-16 | 北京工业大学 | Normal-temperature synthesis method for polycarboxylic acid water-reducing agent |
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| CN107759126A (en) * | 2017-10-10 | 2018-03-06 | 江苏苏博特新材料股份有限公司 | A kind of gunite concrete water reducer and preparation method thereof |
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