CN104497230A - Ester-ether copolymerization type polycarboxylate superplasticizer as well as preparation method and application thereof - Google Patents
Ester-ether copolymerization type polycarboxylate superplasticizer as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an ester-ether copolymerization type polycarboxylate superplasticizer which is characterized in that the structural formula is as shown in the specification, in the formula, a and b are greater than 0, c is greater than or equal to 0, 0n is less than d and is greater than 0, M1 is of a polyethylene glycol monomethyl ether structure, M2 is one of alkali metal atoms and H atoms or both the alkali metal atoms and the H atoms, M3 is one of alkali metal atoms and H atoms or both the alkali metal atoms and the H atoms, and M4 is of an ether monomer structure.
Description
Technical field
The present invention relates to a kind of ester ether copoly type polycarboxylate water-reducer, Preparation Method And The Use.
Background technology
Polycarboxylate water-reducer is also known as superplasticizer (Superplasticizer), use the most extensive, consumption is maximum a kind of concrete admixture at present, applied for a patent in the eighties in 20th century by Japanese Kao company the earliest, through the development in more than ten years, progressively replace traditional naphthalene water reducer and lignin water reducer.The article of the relevant polycarboxylate water-reducer performance that Japanese scholars in 1985 is delivered is at present the earliest about the document of polycarboxylate water-reducer synthetic method, and the document have studied carboxylic serials reactive polymer for controlling slump loss.Japan started to promote polycarboxylate water-reducer the nineties in 20th century.The just research of initial polycarboxylate water-reducer mainly concentrates on the research of esters monomer as reaction raw materials, the synthesis of such polycarboxylate water-reducer is generally two reaction process, namely first by having carboxylic acid and the polyoxyethylene glycol generation esterification of reactive behavior double bond, synthesize double bond containing ester PEGlike coating monomer, then the raw materials such as itself and double bond containing carboxylic acid, sulfonic compound are carried out Raolical polymerizable.Be limited to the factors such as alternative raw material type is less, reaction conditions is single, the mechanism of action is distinct not, analysis means imperfection, make the kind of early stage polycarboxylate water-reducer less.After nineteen ninety-five, exceed naphthalene water reducer at the consumption of Japanese polycarboxylate water-reducer.Along with polycarboxylate water-reducer use range is constantly expanded, consumption constantly increases, and its correlative study becomes focus gradually.After 2000, the ether type monomer technology of synthesizing with double bond is ripe gradually, has occurred the bibliographical information of one-step synthesis method poly carboxylic acid.
The research of professor J.Plank to polycarboxylate water-reducer adsorption process shows, esters monomer absorption is very fast, and initial water-reducing rate is higher, but due to loss too fast, often protect the retarding effect that collapses poor; Ether type monomer physical property is more stable in the basic conditions, and is not vulnerable to the impact of cement granules electric charge, and absorption consumes comparatively slow, thus through time function of slump protection be better than ester class polycarboxylate water-reducer.
The research of domestic polycarboxylate water-reducer is started late, and product performance and Foreign Advanced Lerel still have certain gap, but also has numerous academy's successes to emerge in large numbers in recent years.Professor Li Chongzhi of Tsing-Hua University first with polyoxyethylene glycol, maleic anhydride for raw material, by esterification synthesizing polyethylene glycol maleate monomer, and its performance is measured; The Ran Qian equality of Jiangsu research institute of building materials, according to the absorption dispersing property of water reducer, has synthesized main chain simultaneously with negatively charged ion and cationic PACP water reducer; The Qiu Xueqing of South China Science & Engineering University etc. think the shorter polycarboxylate water-reducer dispersing property of polyethylene oxide side chains poor be that polyethylene oxide side chains is longer, and side chain may be made mutually to be wound around because sterically hindered effect is less, hinder water reducer unfolding in the solution.
Domesticly at present still have a great deal of construction work using the water reducer of non-polycarboxylic acid, although these conventional water reducing agents by composite can improving performance within the specific limits, cannot meet the needs of high-grade concrete.And increasing construction work can propose high requirement to polycarboxylate water-reducer initial performance and time dependent simultaneously, be often difficult to be solved by preparation method in current Practical Project.
Summary of the invention
One of them object of the present invention is to overcome deficiency of the prior art, provides a kind of ester ether copoly type polycarboxylate water-reducer.
For realizing above object, the present invention is achieved through the following technical solutions:
A kind of ester ether copoly type polycarboxylate water-reducer, it is characterized in that, its structural formula is:
Wherein a, b > 0, c >=0; D > 0n > 0
M
1mPEG-550 structure;
M
2for the wherein a kind of of alkali metal atom or H atom or exist simultaneously;
M
3for the wherein a kind of of alkali metal atom or H atom or exist simultaneously;
M
4for ether type monomer structure.
Preferably, in described molecular formula, each repeating unit is block distributed.
Another object of the present invention is to overcome deficiency of the prior art, provides a kind of preparation method of ester ether copoly type polycarboxylate water-reducer.
For realizing above object, the present invention is achieved through the following technical solutions:
The preparation method of described ester ether copoly type polycarboxylate water-reducer, is characterized in that, the common and unsaturated carboxylic acid copolyreaction of step (1), esters monomer and ether type monomer forms.
Preferably, described ether type monomer is modified polyether methylpropenyl polyethers or propenyl polyoxyethylene glycol.
Preferably, described esters monomer is acrylic or methacrylic acid and the esterification products of polyoxyethylene glycol (PEG) or the esterification products of vinylformic acid, methacrylic acid and MPEG-550 (MPEG).
Preferably, described unsaturated carboxylic acid is vinylformic acid, methacrylic acid, maleic anhydride, fumaric acid.
Preferably, described esters monomer is that polyethers or polyalcohols and unsaturated carboxylic acid esterification are reacted and formed.
Preferably, described alcohol is polyoxyethylene glycol; Described ether is MPEG-550.
Preferably, described unsaturated carboxylic acid is selected from acrylic or methacrylic acid.
Preferably, described polyethers is selected from allyl polyglycol, molecular weight ranges 600 ~ 3000 or modified polyether, molecular weight ranges 800 ~ 4000.
Preferably, described esterification reaction under chain-transfer agent participates in.
Preferably, described esterification also reaction under one or both of initiator and stopper participate in.
Preferably, the temperature of reaction of described step (2) is 70 DEG C-90 DEG C.
Preferably, the mol ratio of esterification carboxylic acid mole number and polyethers is greater than 1.2; Initiator amount is the 0.5%-3.0% of reactant quality; Stopper consumption is the 0.01%-0.1% of reactant total mass.
Preferably, in described step (2), also in reactant, the chain-transfer agent aqueous solution is added, as Thiovanic acid, thiohydracrylic acid, sodium allylsulfonate, methylpropene sodium sulfonate etc.
Preferably, the temperature of reaction of described copolyreaction is 50 DEG C-80 DEG C
Preferably, described copolyreaction reaction under chain-transfer agent participates in.
Preferably, described chain-transfer agent is Thioglycolic acid or thin base propionic acid.
Preferably, described copolyreaction for react under persulfate initiator.
Preferably, in copolyreaction, the ratio of each raw material is:
The ratio that esters monomer mole number accounts for total moles monomer is 0.2 ~ 0.8;
The ratio that ether type monomer mole number accounts for total moles monomer is 0.3 ~ 0.7;
The ratio of carboxylic acid mole number and total monomer mole number is 2.0 ~ 5.5;
Over cure acids initiator amount is 0.2% ~ 2.0% of reactant total mass;
Sulfydryl class chain-transfer agent consumption is 0.1% ~ 1.0% of reactant total mass.
Preferably, in described step (2), the sulfonate containing double bond is also added.
Preferably, the sulfonate containing double bond is selected from sodium allylsulfonate, methylpropene sodium sulfonate or 2-acrylamide-2-methyl propane sulfonic.
Preferably, after step (2) react, then reactant to be neutralized to pH value be 6-8, adjusts solid content to 20%-40%.
Another object of the present invention is to overcome deficiency of the prior art, provides a kind of purposes of ester ether copoly type polycarboxylate water-reducer.
For realizing above object, the present invention is achieved through the following technical solutions:
The purposes of aforementioned ester ether copoly type polycarboxylate water-reducer in cement.
Beneficial effect of the present invention is:
1. the present invention is used for high performance water-reducer with time esters monomer and ether type monomer, prepare a kind of have concurrently initial high water reducing rate with through time function of slump protection polycarboxylate water-reducer.
2. the ester ether copoly type polycarboxylate water-reducer over-all properties of the present invention's synthesis is better than the water reducer only by ester class or ethers synthesis.
Accompanying drawing explanation
Fig. 1 is the liquid chromatogram that vinylformic acid and thiohydracrylic acid start to drip material composition in front reaction system.
Fig. 2 is the liquid chromatogram of the synthetic product system after reaction terminates.
Embodiment
Ester ether copoly type polycarboxylate water-reducer provided by the present invention, in a kind of preferred embodiment of described water reducer, be prepared into the sample that solids content is preferably 30 ~ 40%, and by high performance liquid chromatography (HPLC), its raw material residual quantity is measured, to prove that esters monomer and ether type monomer all have effect and participate in polyreaction, generate the polycarboxylate water-reducer simultaneously comprising above-mentioned two kinds of side-chain structures.
The preparation method of ester ether copoly type polycarboxylate water-reducer of the present invention, described method comprises the steps:
Illustrate that the preparation method of ester ether copoly type type polycarboxylate water-reducer comprises the steps:
1) esters monomer synthesis:
This step be different molecular weight polyoxyethylene glycol (PEG) (600 ~ 3000) or MPEG-550 (MPEG) (1000 ~ 4000) under certain reaction conditions with unsaturated carboxylic acid generation esterification, the esterification products of PEG or the esterification products of MPEG can be generated respectively.
Unsaturated carboxylic acid selected by this patent synthesis PEG esterification products can be vinylformic acid, methacrylic acid (intermolecular cross-linking can be caused to cause molecular weight excessive if select maleic anhydride and PEG to carry out esterification); Synthesis PMEG unsaturated acid used is vinylformic acid, methacrylic acid, maleic anhydride, methylene-succinic acid etc.Polyether monomer used can be allyl polyglycol (APEG), molecular weight ranges 600 ~ 3000 or modified polyether (TPEG) molecular weight ranges 800 ~ 4000; Other polar monomers are the unsaturated sulfonic acid salt containing double bond, as methylpropene sodium sulfonate, propenyl sodium sulfonate.Unsaturated sulfonic acid salt both in order to introduce polar group sulfonic group, also played chain-transfer agent effect.
Add in reaction vessel and necessarily measure PEG (technical grade) or MPEG (technical grade), unsaturated carboxylic acid (AR level) through processed, mechanical stirring evenly makes it to form homogeneous solution, add a certain amount of tosic acid and Resorcinol, react 3 ~ 6 hours under 70 ~ 90 DEG C of reaction conditionss, toluene can be added as water entrainer to improve esterification yield if needed.
After esterification terminates, esterification products is poured in saturated salt solution (magnesium chloride, sodium-chlor or sodium sulfate etc.), stir, add ethyl acetate again, after vigorous stirring, treat its stratification, retain upper strata ethyl acetate layer, lower floor is at least extracting 2 times by ethyl acetate, merge above-mentioned ethyl acetate, underpressure distillation after dewatering by anhydrous sodium sulphate, Separation and Recovery ethyl acetate, use in order to recirculation, the light brown liquid retained after distillation is esterification products.
Measure esterification products material composition by high performance liquid chromatography (HPLC), when taking MPEG as reaction raw materials, esterification yield is 86% ~ 92%; When taking PEG as reaction raw materials, nonesterified PEG is 3.5 ~ 5.5%, and all the other materials are monoesters or the dibasic acid esters of PEG, and temperature of reaction is higher, dibasic acid esters ratio is larger in larger the generated product of initiator amount.
Its reaction raw materials ratio is:
Esterification carboxylic acid mole number and MPEG mole number ratio are greater than 1.2, and if polyethers used is PEG, owing to there being dibasic acid esters to generate, carboxylic acid and PEG mol ratio should be greater than 2.1, as to ensure esterification yield;
Initiator amount is 0.5% ~ 3.0% of reactant quality;
Hydroquinone of polymerization retarder consumption is 0.01% ~ 0.1% of reactant total mass.
2) synthesis of ester ether copoly type polycarboxylate water-reducer
Radical polymerization step reaction temperature of the present invention is at 50 ~ 80 DEG C, hydrogen peroxide can decompose in this temperature rapidly thus cannot produce free radical, therefore the present invention's initiator used is persulfuric acid salt, can be the mixing etc. of one or more in Sodium Persulfate, Potassium Persulphate or ammonium persulphate.
Step 1 is added according to metered proportions in reaction vessel) the ester class polyether monomer prepared, polyether monomer (APEG or TPEG) and the sulfonate containing double bond are (as sodium allylsulfonate, methylpropene sodium sulfonate, 2-acrylamide-2-methyl propane sulfonic etc.), add distilled water, mechanical stirring under 50 ~ 80 DEG C of temperature of reaction, after adding over cure acids initiator, constant speed drips unsaturated carboxylic acid solution (vinylformic acid respectively, methacrylic acid, maleic anhydride etc.) and the chain-transfer agent aqueous solution (Thiovanic acid or thiohydracrylic acid), time for adding controls at 90 ~ 180min, dropwise stopped reaction after rear continuation reaction 1 ~ 3h, obtain copolymerization product,
Polyreaction material rate is:
The ratio that esters monomer mole number accounts for total moles monomer is 0.2 ~ 0.8;
The ratio that ether type monomer mole number accounts for total moles monomer is 0.3 ~ 0.7;
The ratio of carboxylic acid mole number and total monomer mole number is 2.0 ~ 5.5;
Over cure acids initiator amount is 0.2% ~ 2.0% of reactant total mass;
Sulfydryl class chain-transfer agent consumption is 0.1% ~ 1.0% of reactant total mass.
3) in and aftertreatment: by step 2) prepared by ester ether copoly type polycarboxylic acid polymer add alkaline solution and be neutralized to 6 ~ 8, adjustment solid content to 20% ~ 40%, namely obtain the polycarboxylate water-reducer simultaneously containing ester groups and ethers group.
The present invention uses unsaturated sulfonic acid salt to be, owing to himself there being certain chain-transfer agent effect, thus suitably can reduce the consumption of sulfydryl class chain-transfer agent as reaction raw materials.
Below in conjunction with embodiment, the present invention is further described.
Embodiment 1:
MPEG-550 (MPEG) 120g of molecular weight 1200 and vinylformic acid 120g is added in reaction vessel, add tosic acid 5.0g and Resorcinol 0.5g, after stirring, be warming up to 85 DEG C, stirring and refluxing reaction 5h, more than measured value rate >=90%, stop heating.
The saturated NaCl solution of 200ml will be added in above-mentioned reactant, 200ml ethyl acetate is added after vigorous stirring, stratification or ultrasonic layering after vigorous stirring, retain upper strata ethyl acetate layer, repeat to be extracted with ethyl acetate 2 times again, merge the ethyl acetate layer of 3 extractions, ethyl acetate is removed in underpressure distillation, obtains ester class polymeric monomer.
The above-mentioned modified polyether (TPEG) preparing esters monomer 100g and 150g molecular weight 2400 is added reaction vessel, add 200g distilled water, stirring is warming up to 60 ~ 70 DEG C, add initiator Sodium Persulfate 5.0g, to be mixed evenly after start the 5wt% solution 40g dripping vinylformic acid 55.0g and chain-transfer agent Thiovanic acid, time for adding 180min, dropwises rear continuation reaction 60min.Sodium hydroxide solution with 30% regulates pH value to 6 ~ 7, is diluted with water to 40%, is ester ether copoly type polycarboxylate water-reducer.
Embodiment 2:
MPEG-550 (MPEG) 240g of molecular weight 2400 and vinylformic acid 120g is added in reaction vessel, add tosic acid 7.5g and Resorcinol 0.75g, after stirring, be warming up to 85 DEG C, stirring and refluxing reaction 5h, more than measured value rate >=90%, stop heating.
The saturated NaCl solution of 200ml will be added in above-mentioned reactant, 200ml ethyl acetate is added after vigorous stirring, stratification or ultrasonic layering after vigorous stirring, retain upper strata ethyl acetate layer, repeat to be extracted with ethyl acetate 2 times again, merge the ethyl acetate layer of 3 extractions, ethyl acetate is removed in underpressure distillation, obtains ester class polymeric monomer.
The above-mentioned modified polyether (TPEG) preparing esters monomer 200g and 150g molecular weight 2400 is added reaction vessel, add 200g distilled water, stirring is warming up to 60 ~ 70 DEG C, add initiator Sodium Persulfate 5.0g, to be mixed evenly after start the 5wt% solution 40g dripping vinylformic acid 55.0g and chain-transfer agent Thiovanic acid, time for adding 180min, dropwises rear continuation reaction 60min.Sodium hydroxide solution with 30% regulates pH value to 6 ~ 7, is diluted with water to 40%, is ester ether copoly type polycarboxylate water-reducer.
Embodiment 3:
Polyoxyethylene glycol (PEG) 120g of molecular weight 1200 and vinylformic acid 240g is added in reaction vessel, add tosic acid 5.0g and Resorcinol 0.5g, after stirring, be warming up to 85 DEG C, stirring and refluxing reaction 5h, more than measured value rate >=90%, stop heating.
The saturated metabisulfite solution of 200ml will be added in above-mentioned reactant, 200ml ethyl acetate is added after vigorous stirring, stratification or ultrasonic layering after vigorous stirring, retain upper strata ethyl acetate layer, repeat to be extracted with ethyl acetate 2 times again, merge the ethyl acetate layer of 3 extractions, ethyl acetate is removed in underpressure distillation, obtains ester class polymeric monomer.
The above-mentioned modified polyether (TPEG) preparing esters monomer 100g and 150g molecular weight 2400 is added reaction vessel, add 200g distilled water, stirring is warming up to 60 ~ 70 DEG C, add initiator Sodium Persulfate 5.0g, to be mixed evenly after start the 5wt% solution 40g dripping vinylformic acid 55.0g and chain-transfer agent Thiovanic acid, time for adding 180min, dropwises rear continuation reaction 60min.Sodium hydroxide solution with 30% regulates pH value to 6 ~ 7, is diluted with water to 40%, is ester ether copoly type polycarboxylate water-reducer.
Embodiment 4:
MPEG-550 (MPEG) 120g of molecular weight 1200 and vinylformic acid 120g is added in reaction vessel, add tosic acid 5.0g and Resorcinol 0.5g, after stirring, be warming up to 85 DEG C, stirring and refluxing reaction 5h, more than measured value rate >=90%, stop heating.
The saturated NaCl solution of 200ml will be added in above-mentioned reactant, 200ml ethyl acetate is added after vigorous stirring, stratification or ultrasonic layering after vigorous stirring, retain upper strata ethyl acetate layer, repeat to be extracted with ethyl acetate 2 times again, merge the ethyl acetate layer of 3 extractions, ethyl acetate is removed in underpressure distillation, obtains ester class polymeric monomer.
The above-mentioned modified polyether (TPEG) preparing esters monomer 100g and 150g molecular weight 2400 is added reaction vessel, add 200g distilled water and 25g methylpropene sodium sulfonate (MAS), stirring is warming up to 65 DEG C, add initiator Sodium Persulfate 6.0g, to be mixed evenly after start the 5wt% solution 40g dripping vinylformic acid 50.0g and chain-transfer agent Thiovanic acid, time for adding 240min, dropwises rear continuation reaction 60min.Sodium hydroxide solution with 30% regulates pH value to 6 ~ 7, is diluted with water to 40%, is ester ether copoly type polycarboxylate water-reducer.
Embodiment 5:
MPEG-550 (MPEG) 120g of molecular weight 1200 and methacrylic acid 140g is added in reaction vessel, add tosic acid 6.0g and Resorcinol 0.6g, add 200ml toluene as reflux solvent, stirring makes it about 110 DEG C back flow reaction, stirring and refluxing reaction 5h, more than measured value rate >=95%, stop heating.
The saturated sodium nitrate solution of 200ml will be added in above-mentioned reactant, 200ml ethyl acetate is added after vigorous stirring, stratification or ultrasonic layering after vigorous stirring, retain upper strata ethyl acetate layer, repeat to be extracted with ethyl acetate 2 times again, merge the ethyl acetate layer of 3 extractions, ethyl acetate is removed in underpressure distillation, obtains ester class polymeric monomer.
The above-mentioned modified polyether (TPEG) preparing esters monomer 100g and 150g molecular weight 2400 is added reaction vessel, add 200g distilled water, stirring is warming up to 60 ~ 70 DEG C, add initiator Sodium Persulfate 5.0g, to be mixed evenly after start the 5wt% solution 40g dripping methacrylic acid 65.0g and chain-transfer agent Thiovanic acid, time for adding 180min, dropwises rear continuation reaction 60min.Sodium hydroxide solution with 30% regulates pH value to 6 ~ 7, is diluted with water to 40%, is ester ether copoly type polycarboxylate water-reducer.
The sign of product
Analysis and characterization is carried out by the ester ether copoly type polycarboxylate water-reducer of high performance liquid chromatography (HPLC) to synthesis, if esterification monomer product is without steps such as extraction brine, can containing residual carboxylic acid monomer in esters monomer, affect material ratio during follow-up high performance water-reducer, by the purification process of this patent, namely can realize obtaining comparatively pure esters monomer object, recycling can be carried out to organic solvent ethyl acetate used again, reduce corresponding cost.
In addition by efficient liquid phase chromatographic analysis, in the water reducer after reaction terminates, esters monomer residual quantity is less than 1.5%; Ether type monomer residual quantity is less than 3.5%, reaches the object that monomer fully reacts, and synthesized ester ether copoly type polycarboxylate water-reducer effective constituent meets the requirements.
Fig. 1 is the liquid chromatogram that vinylformic acid and thiohydracrylic acid start to drip material composition in front reaction system.The mol ratio of ether type monomer used and esters monomer is 1:1, and liquid phase chromatographic analysis condition used is acetonitrile: water=40:60, and detector used is evaporative light detector.By liquid chromatography, material composition is analyzed, appearance time be the chromatographic peak of 2.398min corresponding for esters monomer, appearance time is the ether type monomer that the chromatographic peak of 5.199min is corresponding.
Fig. 2 is the liquid chromatogram of the synthetic product system after reaction terminates, appearance time is the chromatographic peak of 1.412min is the ester ether copoly type polycarboxylate water-reducer that free radicals copolymerization reaction synthesizes, monomer conversion > 96%, the chromatographic peak of 2.574min is the chromatographic peak of unreacted esters monomer, and the chromatographic peak of 5.043min is the chromatographic peak of unreacted ether type monomer.Chromatogram is analyzed, ester ether copoly type polycarboxylate water-reducer simultaneously using esters monomer and ether type monomer as reaction raw materials, the transformation efficiency of two kinds of monomers all meets expection.
The invention has the beneficial effects as follows:
1. the present invention is used for high performance water-reducer with time esters monomer and ether type monomer, prepare a kind of have concurrently initial high water reducing rate with through time function of slump protection polycarboxylate water-reducer;
2. the ester ether copoly type polycarboxylate water-reducer over-all properties of the present invention's synthesis is better than the water reducer only by ester class or ethers synthesis
Test respectively identical mole number carboxylic acid and polymeric monomer, under the same conditions synthesize only with esters monomer, only with ether type monomer and the polycarboxylate water-reducer using esters monomer and ether type monomer simultaneously.Testing cement used is Shanghai conch 42.5 ordinary portland cement, tests cement paste mobility with reference to GB/8076-2008, and degree of mobilization expansion diameter units is millimeter (mm), and experimental result is as follows:
| Initially | 30min | 60min | 90min | 120min | 180min | |
| Esters monomer water reducer | 288 | 275 | 268 | 244 | 220 | 175 |
| Ether type monomer water reducer | 275 | 272 | 265 | 257 | 245 | 225 |
| Ester ether copoly type water reducer (example 1) | 293 | 287 | 279 | 270 | 261 | 249 |
| Ester ether copoly type water reducer (example 5) | 290 | 288 | 284 | 273 | 265 | 253 |
Proved by pulp flowage test result, under the same terms, ester ether copoly type polycarboxylate water-reducer has esters monomer side chain and ether type monomer side chain in its structural unit simultaneously, thus there is the two advantage simultaneously, there is initial water-reducing rate preferably, have again good guarantor to collapse effect, its through time slump-loss to be less than only esters monomer be the polycarboxylate water-reducer of Material synthesis.
By gel permeation chromatography (GPC), the diminishing molecular weight containing ester group and ether is analyzed, its number-average molecular weight and weight-average molecular weight all with the same terms under with polyether monomer be completely raw material water reducer sample close, and without obvious monomer residue, various reaction raw materials all reacts comparatively complete.
After testing, all the other embodiments of the present invention can reach and embodiment 1,5 identical effects.
Beneficial effect of the present invention is:
1. the present invention is used for high performance water-reducer with time esters monomer and ether type monomer, prepare a kind of have concurrently initial high water reducing rate with through time function of slump protection polycarboxylate water-reducer.
2. the ester ether copoly type polycarboxylate water-reducer over-all properties of the present invention's synthesis is better than the water reducer only by ester class or ethers synthesis.
Embodiment in the present invention, only for the present invention will be described, does not form the restriction to right, other equivalent in fact substituting, all in scope that those skilled in that art can expect.
Claims (24)
1. an ester ether copoly type polycarboxylate water-reducer, is characterized in that, its structural formula is:
Wherein a, b > 0, c >=0; D > 0n > 0
M
1mPEG-550 structure;
M
2for the wherein a kind of of alkali metal atom or H atom or exist simultaneously;
M
3for the wherein a kind of of alkali metal atom or H atom or exist simultaneously;
M
4for ether type monomer structure.
2. ester ether copoly type polycarboxylate water-reducer according to claim 1, it is characterized in that, in described molecular formula, each repeating unit is block distributed.
3. the preparation method of the ester ether copoly type polycarboxylate water-reducer described in claim 1 or 2, is characterized in that, the common and unsaturated carboxylic acid copolyreaction of step (1), esters monomer and ether type monomer forms.
4. the preparation method of ester ether copoly type polycarboxylate water-reducer according to claim 3, is characterized in that, described ether type monomer is modified polyether methylpropenyl polyethers or propenyl polyoxyethylene glycol.
5. the preparation method of ester ether copoly type polycarboxylate water-reducer according to claim 3, it is characterized in that, described esters monomer is acrylic or methacrylic acid and the esterification products of polyoxyethylene glycol (PEG) or the esterification products of vinylformic acid, methacrylic acid and MPEG-550 (MPEG).
6. the preparation method of ester ether copoly type polycarboxylate water-reducer according to claim 3, it is characterized in that, described unsaturated carboxylic acid is vinylformic acid, methacrylic acid, maleic anhydride, fumaric acid.
7. the preparation method of ester ether copoly type polycarboxylate water-reducer according to claim 3, is characterized in that, described esters monomer is that polyethers or polyalcohols and unsaturated carboxylic acid esterification are reacted and formed.
8. the preparation method of ester ether copoly type polycarboxylate water-reducer according to claim 7, it is characterized in that, described alcohol is polyoxyethylene glycol; Described ether is MPEG-550.
9. the preparation method of ester ether copoly type polycarboxylate water-reducer according to claim 7, it is characterized in that, described unsaturated carboxylic acid is selected from acrylic or methacrylic acid.
10. the preparation method of ester ether copoly type polycarboxylate water-reducer according to claim 7, it is characterized in that, described polyethers is selected from allyl polyglycol, molecular weight ranges 600 ~ 3000 or modified polyether, molecular weight ranges 800 ~ 4000.
The preparation method of 11. ester ether copoly type polycarboxylate water-reducers according to claim 7, is characterized in that, described esterification is reaction under chain-transfer agent participates in.
The preparation method of 12. ester ether copoly type polycarboxylate water-reducers according to claim 7, is characterized in that, described esterification is reaction under one or both of initiator and stopper participate in also.
The preparation method of 13. ester ether copoly type polycarboxylate water-reducers according to claim 7, it is characterized in that, the temperature of reaction of described step (2) is 70 DEG C-90 DEG C.
The preparation method of 14. ester ether copoly type polycarboxylate water-reducers according to claim 7, it is characterized in that, the mol ratio of esterification carboxylic acid mole number and polyethers is greater than 1.2;
Initiator amount is 0.5% ~ 3.0% of reactant quality;
Stopper consumption is 0.01% ~ 0.1% of reactant total mass.
The preparation method of 15. ester ether copoly type polycarboxylate water-reducers according to claim 4, it is characterized in that, in described step (2), also in reactant, add the chain-transfer agent aqueous solution, as Thiovanic acid, thiohydracrylic acid, sodium allylsulfonate, methylpropene sodium sulfonate etc.
The preparation method of 16. ester ether copoly type polycarboxylate water-reducers according to claim 3, it is characterized in that, the temperature of reaction of described copolyreaction is 50 DEG C-80 DEG C.
The preparation method of 17. ester ether copoly type polycarboxylate water-reducers according to claim 3, is characterized in that, described copolyreaction is reaction under chain-transfer agent participates in.
The preparation method of 18. ester ether copoly type polycarboxylate water-reducers according to claim 11 or 17, it is characterized in that, described chain-transfer agent is Thioglycolic acid or thin base propionic acid.
The preparation method of 19. ester ether copoly type polycarboxylate water-reducers according to claim 3, it is characterized in that, described copolyreaction for react under persulfate initiator.
The preparation method of 20. ester ether copoly type polycarboxylate water-reducers according to claim 3, it is characterized in that, in copolyreaction, the ratio of each raw material is:
The ratio that esters monomer mole number accounts for total moles monomer is 0.2 ~ 0.8;
The ratio that ether type monomer mole number accounts for total moles monomer is 0.3 ~ 0.7;
The ratio of carboxylic acid mole number and total monomer mole number is 2.0 ~ 5.5;
Over cure acids initiator amount is 0.2% ~ 2.0% of reactant total mass;
Sulfydryl class chain-transfer agent consumption is 0.1% ~ 1.0% of reactant total mass.
The preparation method of 21. ester ether copoly type polycarboxylate water-reducers according to claim 3, is characterized in that, in described step (2), also add the sulfonate containing double bond.
The preparation method of 22. ester ether copoly type polycarboxylate water-reducers according to claim 20, it is characterized in that, the sulfonate containing double bond is selected from sodium allylsulfonate, methylpropene sodium sulfonate or 2-acrylamide-2-methyl propane sulfonic.
The preparation method of 23. ester ether copoly type polycarboxylate water-reducers according to claim 3, is characterized in that, after step (2) has been reacted, then reactant to be neutralized to pH value be 6-8, and adjustment solid content is to 20%-40%.
The purposes of ester ether copoly type polycarboxylate water-reducer in cement described in 24. claims 1 or 2.
Priority Applications (1)
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105037658A (en) * | 2015-07-03 | 2015-11-11 | 上海台界化工有限公司 | Preparation method of polycarboxylate water reducer with intensively-distributed carboxyl groups and high water reduction performance, product thereof, and application of product |
| CN105174782A (en) * | 2015-09-02 | 2015-12-23 | 马清浩 | Ether ester type water reducer and preparation method thereof |
| CN105254201A (en) * | 2015-09-02 | 2016-01-20 | 马清沛 | Early strength polyether ester water reducer and preparation method thereof |
| CN106146759A (en) * | 2015-04-09 | 2016-11-23 | 张耀忠 | A kind of high-performance polycarboxylic acids water reducing agent and preparation method thereof |
| CN110105504A (en) * | 2019-05-27 | 2019-08-09 | 马清浩 | A kind of high-thin arch dam slow-setting polycarboxylic acid water reducing agent and its preparation and application |
| CN114702273A (en) * | 2019-12-24 | 2022-07-05 | 科之杰新材料集团福建有限公司 | Polycarboxylate superplasticizer for reinforcing steel bar sleeve grouting material for prefabricated part and grouting material thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101205127A (en) * | 2007-11-21 | 2008-06-25 | 厦门市建筑科学研究院集团股份有限公司 | Formula of sustained release type polycarboxylic acid series high-performance dehydragent and method for manufacturing same |
| CN101357833A (en) * | 2008-08-22 | 2009-02-04 | 上海三瑞高分子材料有限公司 | Slump retaining polyocarboxy acid superplasticiser |
| CN101708973A (en) * | 2009-11-04 | 2010-05-19 | 山东华伟银凯建材有限公司 | Water-plastic retaining polycarboxylic acid water reducer and method for preparing same |
| CN101955333A (en) * | 2010-10-12 | 2011-01-26 | 同济大学 | Poly carboxylic acid series water reducing agent with low content and high water-reducing rate, synthetic method and use method thereof |
| CN102660037A (en) * | 2012-04-11 | 2012-09-12 | 长沙加美乐素化工有限公司 | Preparation method of super-sustained release ester-ether crosslinking polycarboxylic acid water reducer |
| CN104140503A (en) * | 2014-07-30 | 2014-11-12 | 江西格雷斯科技股份有限公司 | Method for synthesizing high-water-reduction high-slump-retaining high-performance polycarboxylate water reducer at normal temperature |
-
2014
- 2014-12-16 CN CN201410782664.8A patent/CN104497230A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101205127A (en) * | 2007-11-21 | 2008-06-25 | 厦门市建筑科学研究院集团股份有限公司 | Formula of sustained release type polycarboxylic acid series high-performance dehydragent and method for manufacturing same |
| CN101357833A (en) * | 2008-08-22 | 2009-02-04 | 上海三瑞高分子材料有限公司 | Slump retaining polyocarboxy acid superplasticiser |
| CN101708973A (en) * | 2009-11-04 | 2010-05-19 | 山东华伟银凯建材有限公司 | Water-plastic retaining polycarboxylic acid water reducer and method for preparing same |
| CN101955333A (en) * | 2010-10-12 | 2011-01-26 | 同济大学 | Poly carboxylic acid series water reducing agent with low content and high water-reducing rate, synthetic method and use method thereof |
| CN102660037A (en) * | 2012-04-11 | 2012-09-12 | 长沙加美乐素化工有限公司 | Preparation method of super-sustained release ester-ether crosslinking polycarboxylic acid water reducer |
| CN104140503A (en) * | 2014-07-30 | 2014-11-12 | 江西格雷斯科技股份有限公司 | Method for synthesizing high-water-reduction high-slump-retaining high-performance polycarboxylate water reducer at normal temperature |
Non-Patent Citations (1)
| Title |
|---|
| 中国建筑学会建材分会混凝土外加剂应用技术专业委员会: "《聚羧酸系高性能减水剂及其应用技术新进展》", 31 May 2011, 北京理工大学出版社 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106146759A (en) * | 2015-04-09 | 2016-11-23 | 张耀忠 | A kind of high-performance polycarboxylic acids water reducing agent and preparation method thereof |
| CN105037658A (en) * | 2015-07-03 | 2015-11-11 | 上海台界化工有限公司 | Preparation method of polycarboxylate water reducer with intensively-distributed carboxyl groups and high water reduction performance, product thereof, and application of product |
| CN105037658B (en) * | 2015-07-03 | 2018-02-23 | 上海台界化工有限公司 | A kind of polycarboxylate water-reducer preparation method, product and the application with high water-reducing property of carboxyl integrated distribution |
| CN105174782A (en) * | 2015-09-02 | 2015-12-23 | 马清浩 | Ether ester type water reducer and preparation method thereof |
| CN105254201A (en) * | 2015-09-02 | 2016-01-20 | 马清沛 | Early strength polyether ester water reducer and preparation method thereof |
| CN105254201B (en) * | 2015-09-02 | 2018-02-16 | 马清沛 | A kind of early-strength polyether ester water reducer and preparation method thereof |
| CN110105504A (en) * | 2019-05-27 | 2019-08-09 | 马清浩 | A kind of high-thin arch dam slow-setting polycarboxylic acid water reducing agent and its preparation and application |
| CN110105504B (en) * | 2019-05-27 | 2021-10-01 | 深圳市五山新材料股份有限公司 | High slump loss resistant retarding polycarboxylate superplasticizer and preparation and application thereof |
| CN114702273A (en) * | 2019-12-24 | 2022-07-05 | 科之杰新材料集团福建有限公司 | Polycarboxylate superplasticizer for reinforcing steel bar sleeve grouting material for prefabricated part and grouting material thereof |
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