CN105175740A - Preparation method of polycarboxylic acid water reducer with high workability - Google Patents
Preparation method of polycarboxylic acid water reducer with high workability Download PDFInfo
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- CN105175740A CN105175740A CN201510526485.2A CN201510526485A CN105175740A CN 105175740 A CN105175740 A CN 105175740A CN 201510526485 A CN201510526485 A CN 201510526485A CN 105175740 A CN105175740 A CN 105175740A
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Abstract
The invention discloses a preparation method of a polycarboxylic acid water reducer with high workability. The preparation method comprises the following steps: mixing acrylic acid with active monomers with high workability, adding an oxidant and co-initiator into the mixture, dropwise adding a mixed solution of unsaturated monomers, chain transferring agent, reducing agent, and water at a low temperature; carrying out reactions to obtain segmented copolymer (intermediate), finally adding methoxy polyethylene glycol and a catalyst to carry out esterification and grafting, and finally neutralizing the products. Through molecular structure design, active monomers with good workability are introduced into polycarboxylic acid water reducer; low temperature polymerization is performed at first, then high temperature esterification is carried out, damage rate of double bonds can be reduced, copolymerization degree is high, and the produced water reducer has good workability and high water reducing rate. The industrial production technology is simple, the production period is largely reduced, and production process is green, environment-friendly, and pollution-free.
Description
Technical field
The invention belongs to the technical field of material of construction, particularly relate to a kind of preparation method of high workability ester class polycarboxylate water-reducer.
Background technology
In recent years, along with the development that China 12 plans, government can drop into substantial contribution, the construction of water conservancy, tunnel, bridge Large Infrastructure Projects for all respects such as infrastructure construction, people's livelihood engineering, environmental protection, and high performance water reducing agent of polyocarboxy acid is still in the middle of a higher market requirement.
Polycarboxylate water-reducer obtains because its raw material supply is convenient, production technique is simple, product is stable and develops faster.But in actual application due to the singularity of domestic a lot of engineering and the change in season obvious, and the sand of different zones, stone material quality are uneven, large containing mud, powder containing quantity difference, the application of a lot of polycarboxylate water-reducer in some engineerings is occurred workability is poor, material is comparatively sticky, the easy poor problem of serviceability such as bleeding.
CN102826784A discloses a kind of polycarboxylate water-reducer and preparation method thereof, by polymeric monomer, unsaturated carboxylic acid, acid amides or acid anhydrides, and insatiable hunger sulfonate monomer, and oxygenant and water, at 45 DEG C, add reductive agent, insulation 3-5 hour, obtain target product with liquid caustic soda neutralization.There is Slump Time losing of Large greatly, the problem of workability difference in the product of this technique.
CN103450411A discloses a kind of preparation method of high-slump-retentionpolycarboxylate polycarboxylate water reducer, first at high temperature with under catalyzer carried out esterification by methoxy poly (ethylene glycol) monomethyl ether and methacrylic acid and obtain esterification polymeric monomer MP, again MP, unsaturated sulfonic acid salt, (methyl) esters of acrylic acid unsaturated monomer and chain-transfer agent are polymerized in aqueous, finally add liquid caustic soda neutralization and obtain target product.The target product workability of this technique is general, and the stopper that esterification process adds has larger impact to polymerization process, and this two-step reaction cycle is longer.
Summary of the invention
Technical problem to be solved by this invention is the preparation method providing a kind of high workability ester class polycarboxylate water-reducer, overcome problems of the prior art and deficiency, thus provide that one has high workability, adaptability is good, dispersing property is excellent, and with short production cycle, the high-performance water reducing agent that technique is simple, environment friendly and pollution-free.
For solving the problems of the technologies described above, technical solution of the present invention is:
A kind of preparation method of high workability ester class polycarboxylate water-reducer comprises the following steps:
(1) by mass parts, 100 parts of vinylformic acid, 2 ~ 10 parts of unsaturated phosphoric acid ester, 2 ~ 8 parts of methacryloxypropyl ethene trimethyl ammonium chlorides and 50 parts of water mix and blends are dissolved and react at 15 DEG C-35 DEG C, add 0.5 ~ 1.0 part of oxygenant and 0.3 ~ 2.0 part of aided initiating successively, drip the mixed solution that formed by 10 ~ 20 parts of vinylformic acid, 0.5 ~ 2.0 part of chain-transfer agent, 0.1 ~ 1.0 part of reductive agent and 50 parts of water again and dropwised in 0.5 ~ 1.0 hour, follow-up continuation of insurance temperature obtains segmented copolymer intermediate in 0.5 hour;
(2) by mass parts, the segmented copolymer intermediate that 100 parts of poly glycol monomethyl ethers, 10 ~ 60 parts of steps 1 are obtained and 0.15 ~ 2 part of catalyst mix, be warming up to 80 DEG C ~ 100 DEG C, stirring and vacuumizing simultaneously makes it react 4 ~ 5 hours under the vacuum tightness of 0.01MPa ~ 0.04MPa, after question response terminates, cool to less than 60 DEG C, add 10 ~ 30 parts of mass concentrations be 30% sodium hydroxide neutralization namely obtain described high workability ester class polycarboxylate water-reducer.
In a preferred embodiment of the invention, described unsaturated phosphoric acid ester is one or both the combination in acrylyl oxy-ethyl phosphoric acid ester, acryloxypropyl phosphoric acid ester, acryloyl-oxy hydroxypropyl phosphorate, methylacryoyloxyethyl phosphoric acid ester, methacryloxypropyl phosphoric acid ester or methacryloxypropyl hydroxypropyl phosphorate.
In a preferred embodiment of the invention, described oxygenant is one or both the combination in hydrogen peroxide, ammonium persulphate, Sodium Persulfate.
In a preferred embodiment of the invention, described aided initiating is one or both the combination in ferrous ammonium sulphate, ferrous sulfate, tetramethyl ammonium chloride.
In a preferred embodiment of the invention, described chain-transfer agent is one or both the combination in mercaptoethanol, Thiovanic acid, 3 ~ thiohydracrylic acid, Dodecyl Mercaptan, thioglycerol, mercaptosuccinic acid.
In a preferred embodiment of the invention, described reductive agent is one or both the combination in L-AA, sodium formaldehyde sulphoxylate, sodium bisulfite.
In a preferred embodiment of the invention, the combination of described macrogol monomethyl ether to be molecular weight be in the macrogol monomethyl ether of 600,1200,2200,3000 any one or two kinds.
In a preferred embodiment of the invention, described catalyzer is solid super-strong acid SO
4 2-/ TiO
2/ La
3+, SO
4 2-/ TiO
2/ Sm
3+, S
2o
8 2-/ ZrO
2wherein one or both combinations.
The preparation method of high workability ester class polycarboxylate water-reducer provided by the invention, adopts Post functionalization grafting, i.e. esterification two step building-up reactions route after first polymerization.Compared to other Patents, this patent has the evident characteristic of the following aspects:
(1) the present invention passes through Molecular Structure Design, introduce the good unsaturated phosphoric acid ester of reactive monomer of workability and methacryloxypropyl ethene trimethyl ammonium chloride, and control segmented copolymer intermediate molecule amount within the scope of 5000-20000, again with poly glycol monomethyl ether esterification, take the method for high temperature esterification after first low temperature polymerization, the method double bond destructive rate is low, and copolymerization degree is high; The product workability obtained is good, water-reducing rate is high, excellent working performance.Compared with the esterification technique in past, without the need to adding stopper during the esterification technique that the present invention relates to being anti-, avoiding and because adding stopper, quality product being had an impact, and production technique is simple, the production cycle shortens greatly, production process environmental protection, pollution-free.
(2) aided initiating adding reductibility can improve copolyreaction activity, Reaction time shorten greatly, improves reaction efficiency.
(3) under the catalysis of solid esterification catalyst, the activation energy of esterification can be reduced, improve speed of reaction, shorten reaction time; And easily separated after completion of the reaction, reusable, to conversion unit and environmental corrosion little.
Following examples are described in further detail the present invention; But the preparation method of a kind of high workability ester class polycarboxylate water-reducer of the present invention is not limited to embodiment.
Embodiment
Embodiment 1
(1) step one: by mass parts, 100 parts of vinylformic acid, 6 parts of acrylyl oxy-ethyl phosphoric acid ester, 3 parts of methacryloxypropyl ethene trimethyl ammonium chlorides and 50 parts of water are placed in reaction unit, stirring and dissolving, 25 DEG C of reactions, 0.8 part of hydrogen peroxide, 0.3 part of ferrous ammonium sulphate and tetramethyl ammonium chloride mixed solution are dropped in reaction unit successively, 10 parts of vinylformic acid, 1.0 parts of 3 ~ thiohydracrylic acids, 0.4 part of L-AA and 50 parts of water are placed in Dropping feeder, within 1.0 hours, dropwise, follow-up continuation of insurance temperature obtains segmented copolymer intermediate in 0.5 hour.
(2) step 2: by mass parts, by 100 parts of poly glycol monomethyl ethers (MPEG-1200), 20 parts of (obtaining in step one) segmented copolymer intermediates, 0.3 part of solid super-strong acid (SO
4 2-/ TiO
2/ La
3+) drop in reaction unit, be warming up to 90 DEG C, stir and vacuumize simultaneously, ensure that vacuum tightness is at 0.02MPa, reacts 4 hours.After question response terminates, cool to less than 60 DEG C, add 10 parts of mass concentrations be 30% sodium hydroxide neutralization obtain certain density high workability ester class polycarboxylate water-reducer.
Embodiment 2
(1) step one: by mass parts, 100 parts of vinylformic acid, 6 parts of acrylyl oxy-ethyl phosphoric acid ester, 3 parts of methacryloxypropyl ethene trimethyl ammonium chlorides and 50 parts of water are placed in reaction unit, stirring and dissolving, 25 DEG C of reactions, 0.8 part of hydrogen peroxide, 0.3 part of ferrous ammonium sulphate and tetramethyl ammonium chloride mixed solution are dropped in reaction unit successively, 10 parts of vinylformic acid, 1.0 parts of 3 ~ thiohydracrylic acids, 0.4 part of L-AA and 50 parts of water are placed in Dropping feeder, within 1.0 hours, dropwise, follow-up continuation of insurance temperature obtains segmented copolymer intermediate in 0.5 hour.
(2) step 2: by mass parts, by 100 parts of poly glycol monomethyl ethers (MPEG-2200), 18 parts of (obtaining in step one) segmented copolymer intermediates, 0.4 part of solid super-strong acid (SO
4 2-/ TiO
2/ La
3+) drop in reaction unit, be warming up to 95 DEG C, stir and vacuumize simultaneously, ensure that vacuum tightness is at 0.01MPa, reacts 5 hours.After question response terminates, cool to less than 60 DEG C, add 10 parts of mass concentrations be 30% sodium hydroxide neutralization obtain certain density high workability ester class polycarboxylate water-reducer.
Embodiment 3
(1) step one: by mass parts, 100 parts of vinylformic acid, 10 parts of methacryloxypropyl hydroxypropyl phosphorate, 5 parts of methacryloxypropyl ethene trimethyl ammonium chlorides and 50 parts of water are placed in reaction unit, stirring and dissolving, 25 DEG C of reactions, 1.0 parts of hydrogen peroxide, 0.3 part of ferrous ammonium sulphate and tetramethyl ammonium chloride mixed solution are dropped in reaction unit successively, 10 parts of vinylformic acid, 0.7 part of 3 ~ thiohydracrylic acid, 0.6 part of L-AA and 50 parts of water are placed in Dropping feeder, within 1.0 hours, dropwise, follow-up continuation of insurance temperature obtains segmented copolymer intermediate in 0.5 hour.
(2) step 2: by mass parts, by 100 parts of poly glycol monomethyl ethers (MPEG-600:MPEG-3000=2:1), 20 parts of (obtaining in step one) segmented copolymer intermediates, 0.4 part of solid super-strong acid (SO
4 2-/ TiO
2/ La
3+) drop in reaction unit, be warming up to 100 DEG C, stir and vacuumize simultaneously, ensure that vacuum tightness is at 0.02MPa, reacts 5 hours.After question response terminates, cool to less than 60 DEG C, add 10 parts of mass concentrations be 30% sodium hydroxide neutralization obtain certain density high workability ester class polycarboxylate water-reducer.
Embodiment 4
(1) step one: by mass parts, 100 parts of vinylformic acid, 8 parts of methacryloxypropyl hydroxypropyl phosphorate, 6 parts of methacryloxypropyl ethene trimethyl ammonium chlorides and 50 parts of water are placed in reaction unit, stirring and dissolving, 25 DEG C of reactions, 1.0 parts of hydrogen peroxide, 0.3 part of ferrous ammonium sulphate and tetramethyl ammonium chloride mixed solution are dropped in reaction unit successively, 10 parts of vinylformic acid, 0.7 part of 3 ~ thiohydracrylic acid, 0.6 part of L-AA and 50 parts of water are placed in Dropping feeder, within 1.0 hours, dropwise, follow-up continuation of insurance temperature obtains segmented copolymer intermediate in 0.5 hour.
(2) step 2: by mass parts, by 100 parts of poly glycol monomethyl ethers (MPEG-2200), 20 parts of (obtaining in step one) segmented copolymer intermediates, 0.4 part of solid super-strong acid (SO
4 2-/ TiO
2/ La
3+) drop in reaction unit, be warming up to 95 DEG C, stir and vacuumize simultaneously, ensure that vacuum tightness is at 0.01MPa, reacts 5 hours.After question response terminates, cool to less than 60 DEG C, add 10 parts of mass concentrations be 30% sodium hydroxide neutralization obtain certain density high workability ester class polycarboxylate water-reducer.
Embodiment 5
Embodiment 5 is the performance tests of the high workability ester class polycarboxylate water-reducer that embodiment 1 ~ 4 obtains.
Embodiment 1 ~ 4 is synthesized the high workability ester class polycarboxylate water-reducer and standard type polycarboxylate water-reducer (HPWR-S) that obtain, adopt standard cement, volume is 0.15% (folding solid part) of glue material amount, according to GB8076-2008 " concrete admixture ", test its concrete water-reducing ratio, the slump and gradual loss.Concrete mix is: water 165Kg, cement 360Kg, and river sand 470Kg, Machine-made Sand 300Kg, stone 1020Kg, it is as shown in the table for acquired results.
Table 1 embodiment performance comparison:
The above; it is only present pre-ferred embodiments; not any restriction is done to technical scope of the present invention, every above embodiment is done according to technical spirit of the present invention any simple modification, equivalent variations and modification, all fall in the protection domain of technical solution of the present invention.
Claims (8)
1. a preparation method for high workability ester class polycarboxylate water-reducer, is characterized in that comprising the following steps:
1) by mass parts, by 100 parts of vinylformic acid, 2 ~ 10 parts of unsaturated phosphoric acid ester, 2 ~ 8 parts of methacryloxypropyl ethene trimethyl ammonium chlorides and 50 parts of water mix and blends dissolve and react at 15 DEG C-35 DEG C, add 0.5 ~ 1.0 part of oxygenant and 0.3 ~ 2.0 part of aided initiating successively, drip by 10 ~ 20 parts of vinylformic acid again, 0.5 ~ 2.0 part of chain-transfer agent, the mixed solution that 0.1 ~ 1.0 part of reductive agent and 50 parts of water are formed also dropwised in 0.5 ~ 1.0 hour, follow-up continuation of insurance temperature obtains segmented copolymer intermediate in 0.5 hour, the molecular weight of wherein said segmented copolymer intermediate is 5000-20000,
2) by mass parts, by 100 parts of poly glycol monomethyl ethers, 10 ~ 60 parts of steps 1) the segmented copolymer intermediate that obtains and 0.15 ~ 2 part of catalyst mix, be warming up to 80 DEG C ~ 100 DEG C, stirring and vacuumizing simultaneously makes it react 4 ~ 5 hours under the vacuum tightness of 0.01MPa ~ 0.04MPa, after question response terminates, cool to less than 60 DEG C, add 10 ~ 30 parts of mass concentrations be 30% sodium hydroxide neutralization namely obtain described high workability ester class polycarboxylate water-reducer.
2. the preparation method of a kind of high workability ester class polycarboxylate water-reducer according to claim 1, is characterized in that: described unsaturated phosphoric acid ester is one or both the combination in acrylyl oxy-ethyl phosphoric acid ester, acryloxypropyl phosphoric acid ester, acryloyl-oxy hydroxypropyl phosphorate, methylacryoyloxyethyl phosphoric acid ester, methacryloxypropyl phosphoric acid ester or methacryloxypropyl hydroxypropyl phosphorate.
3. the preparation method of a kind of high workability ester class polycarboxylate water-reducer according to claim 1, is characterized in that: step 1) in, described oxygenant is one or both the combination in hydrogen peroxide, ammonium persulphate, Sodium Persulfate.
4. the preparation method of a kind of high workability ester class polycarboxylate water-reducer according to claim 1, is characterized in that: step 1) in, described aided initiating is one or both the combination in ferrous ammonium sulphate, ferrous sulfate, tetramethyl ammonium chloride.
5. the preparation method of a kind of high workability ester class polycarboxylate water-reducer according to claim 1, it is characterized in that: step 1) in, described chain-transfer agent is one or both the combination in mercaptoethanol, Thiovanic acid, 3 ~ thiohydracrylic acid, Dodecyl Mercaptan, thioglycerol, mercaptosuccinic acid.
6. the preparation method of a kind of high workability ester class polycarboxylate water-reducer according to claim 1, it is characterized in that: step 1) in, described reductive agent is one or both the combination in L-AA, sodium formaldehyde sulphoxylate, sodium bisulfite.
7. the preparation method of a kind of high workability ester class polycarboxylate water-reducer according to claim 1, is characterized in that: the combination of described macrogol monomethyl ether to be molecular weight be in the macrogol monomethyl ether of 600,1200,2200,3000 any one or two kinds.
8. the preparation method of a kind of high workability ester class polycarboxylate water-reducer according to claim 1, is characterized in that: step 2) in, described catalyzer is solid super-strong acid SO
4 2-/ TiO
2/ La
3+, SO
4 2-/ TiO
2/ Sm
3+, S
2o
8 2-/ ZrO
2wherein one or both combinations.
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Cited By (6)
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| CN105418857A (en) * | 2015-12-31 | 2016-03-23 | 江苏苏博特新材料股份有限公司 | Preparation method and application of polycarboxylate water reducer containing phosphate group |
| CN105837768A (en) * | 2016-05-11 | 2016-08-10 | 合肥工业大学 | Preparation method for polyphosphate water-reducing agent |
| CN106008593A (en) * | 2016-05-26 | 2016-10-12 | 广东复特新型材料科技有限公司 | Unsaturated phosphate ester for producing high-slump-retaining type polycarboxylic acid water reducing agent |
| CN108250343A (en) * | 2016-12-28 | 2018-07-06 | 江苏苏博特新材料股份有限公司 | Compound, research work of air entrained type copolymer and preparation method thereof and the application as concrete rheological modifying agent |
| CN109679108A (en) * | 2018-12-26 | 2019-04-26 | 浙江建研科之杰新材料有限公司 | A kind of preparation method of high water-retaining type polycarboxylate water-reducer |
| CN109790261A (en) * | 2018-12-24 | 2019-05-21 | 科之杰新材料集团有限公司 | A kind of preparation method of block slow-release concrete admixture |
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| CN105418857A (en) * | 2015-12-31 | 2016-03-23 | 江苏苏博特新材料股份有限公司 | Preparation method and application of polycarboxylate water reducer containing phosphate group |
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| CN108250343A (en) * | 2016-12-28 | 2018-07-06 | 江苏苏博特新材料股份有限公司 | Compound, research work of air entrained type copolymer and preparation method thereof and the application as concrete rheological modifying agent |
| CN109790261A (en) * | 2018-12-24 | 2019-05-21 | 科之杰新材料集团有限公司 | A kind of preparation method of block slow-release concrete admixture |
| CN109790261B (en) * | 2018-12-24 | 2021-03-19 | 科之杰新材料集团有限公司 | Preparation method of block slow-release concrete admixture |
| CN109679108A (en) * | 2018-12-26 | 2019-04-26 | 浙江建研科之杰新材料有限公司 | A kind of preparation method of high water-retaining type polycarboxylate water-reducer |
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