CN102746507B - Esterification method in preparing polycarboxylate water reducer - Google Patents
Esterification method in preparing polycarboxylate water reducer Download PDFInfo
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- CN102746507B CN102746507B CN201110108882.XA CN201110108882A CN102746507B CN 102746507 B CN102746507 B CN 102746507B CN 201110108882 A CN201110108882 A CN 201110108882A CN 102746507 B CN102746507 B CN 102746507B
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Abstract
The invention discloses an esterification method in preparing a polycarboxylate water reducer, characterized by using methoxypolyethylene glycol, methacrylic acid or acyclic acid as a raw material, adding the raw material in a reaction vessel, then adding a polymerization inhibitor and a catalyst, stirring, heating to conduct esterification, simultaneously letting 90-130 DEG C dry hot air in the bottom of the reaction vessel through a micropore unit to bring out the moisture generated by the reaction, preserving the heat for 6-10 h, then cooling to 40-50 DEG C and discharging to obtain polyethylene methyl ether methacrylate or polyethylene glycol monomethyl ether methyl acrylate. According to the invention, the method has the advantages of high esterification rate of the reaction system, stable reaction, mild reaction conditions, strong applicability, easiness in operating, and obvious strengths in the fields of environmental protection, energy saving, material consumption reduction and the like, and the reaction can be conducted under normal pressure without pressurized equipment.
Description
Technical field
The present invention relates to the preparation method of polycarboxylic acid water reducer intermediate, particularly relate to a kind of esterification process prepared in polycarboxylate water-reducer, i.e. the preparation method of polyethylene glycol monomethyl ethermethacrylic acid esters or monomethyl polyethylene glycol acrylate ester.
Background technology
Along with the development of concrete technology, have higher requirement to the usefulness of water reducer, in the past traditional water reducer also exists respective shortcoming and defect, and water-reducing rate is low, and protect plasticity is poor, wideless etc. to the adaptability of cement.Since the nineties in 20th century, polycarboxylate water-reducer has developed into a kind of new variety of high efficiency water reducing agent, and it has the excellent properties such as intensity height and thermotolerance, weather resistance, good weatherability.
The preparation of polycarboxylate water-reducer adopts two-step synthesis method more, the first step adopts poly glycol monomethyl ether, methacrylic acid or vinylformic acid are raw material, carry out esterification, generate the polymeric monomer with polymerization activity, and then synthesizing the polycarboxylate water-reducer of polyester, this esterification is the step of crux the most in synthesis technique, and esterification yield is the important factor directly affecting product yield and quality.Esterification is a reversible balanced reaction, and have the generation of water in reaction, the existence of water can affect the skew of chemical equilibrium, and molecular balance is offset to reverse direction, and esterification can not be proceeded, and causes esterification yield not high.
Esterification successfully can be gone on, constantly don't fail to shift out the moisture content in esterification system, but water little for absolute mass is very large from absolute mass, and be again that to shift out this in the system of hydrophilic substance be suitable difficulty.Prior art has: (1) adds the organic solvent of a great deal of, as: benzene, first is stupid, moisture content in esterification body yarn is carried with steaming these solvents, mention in Chinese patent CN1011255113A and adopt poly glycol monomethyl ether and methacrylic acid, under the effect of dispersion train aqua, reaction 6-10 hour, the polycarboxylic acid water reducer macromer of esterification yield more than 99% can be obtained, but this technique needs to adopt water entrainer, about the 40-60% of reactant quality, large usage quantity, increase the complexity of its equipment simultaneously, water entrainer generally volatilizees seriously, be difficult to reclaim, not only increase cost and pollute environment again simultaneously.; (2) pyroprocess and (3) negative pressure method: utilize higher temperature of reaction or quite low negative pressure, impel the material of relatively small molecular weight in reaction mass, carries out moisture content as: (methyl) acrylic acid volatilization.Although the method for these the pasts can impel the carrying out of esterification, improve esterification yield, but also inevitably bring negative impact again, mention in Chinese patent CN101333289, take away the water of esterification generation in esterification reaction process with specific controlled vacuum tightness, thus driving a reaction balance is carried out to positive dirction.Although the reaction conditions described in picture invention is gentle, not with an organic solvent, eliminate the step of aftertreatment, but conversion unit is more complicated, reaction principle be by unreacted methacrylic acid take generate water, just there is the recovery problem of methacrylic acid, simultaneously, methacrylic acid is constantly had to be drawn out of in reaction process, reaction system is unstable, pyroprocess and negative pressure method all can cause the raising of energy consumption and the waste of inventory to strengthen, and also all make corresponding technological process more complicated, also harsher to the requirement of appointed condition.
Summary of the invention
The object of the present invention is to provide a kind of simple to operate, be easy to the esterification process prepared in polycarboxylate water-reducer of control, energy-conserving and environment-protective.
Technical scheme of the present invention is: a kind of esterification process prepared in polycarboxylate water-reducer, with poly glycol monomethyl ether, methacrylic acid or vinylformic acid are raw material, described raw material is added reactor, then poly-resist and catalyzer is added, stir, esterification is carried out in heating, the moisture content that the heated drying air simultaneously passing into 90-130 DEG C through nanopore device in the bottom of reactor produces to take reaction out of, after insulation reaction 6-10 hour, cool to 40-50 DEG C of discharging, obtain polyethylene glycol monomethyl ethermethacrylic acid esters or monomethyl polyethylene glycol acrylate ester.
In a preferred embodiment of the present invention, described poly glycol monomethyl ether molecular weight is 1000-2000.
In a preferred embodiment of the present invention, described poly glycol monomethyl ether and methacrylic acid or acrylic acid mol ratio are 1: 2-4.
In a preferred embodiment of the present invention, described stopper is Resorcinol, para benzoquinone, and one or more mixing in MEHQ or thiophene piperazine, total incorporation accounts for the 0.5%-1.0% of reactant total mass.
In a preferred embodiment of the present invention, described esterifying catalyst is one or more mixing in the vitriol oil, tosic acid, Sulphanilic Acid, and total incorporation accounts for the 2%-4% of reactant total mass.
In a preferred embodiment of the present invention, described heated drying air be by drying treatment after air to add temperature to 90 ~ 130 DEG C of warm air through the preheater of the patterns such as tubulation, coiled pipe, chuck before passing into esterification system.
In a preferred embodiment of the present invention, the air after described drying treatment adopts desiccant-filled instrument air dryer to the dry air processing airflow or the method for swollen evaporation of being splashed again by air compressing post liquefaction is obtained.
In a preferred embodiment of the present invention, described siccative is the one in calcium chloride, Bibulous Silica Gel, sodium hydroxide, potassium hydroxide, active oxidation lithium, the vitriol oil or strong phosphoric acid.
In a preferred embodiment of the present invention, the mode that described heated drying air passes into is for purging reaction system continuously or intermittently.
The present invention adopts the heated drying air passing into 90 ~ 130 DEG C in esterification system, purge the moisture content carried out in esterification system, effectively ensure that carrying out smoothly of esterification, prepare the polycarboxylate water-reducer of excellent performance, ejecta is malaria, avoid the pollution to environment, compared with prior art imitate, reaction system esterification yield of the present invention is high, stable reaction, reaction conditions is gentle, can carry out under normal pressure, do not need pressure exerting device, suitability is strong, easy to operate, in environmental protection, energy-conservation, reduce the aspects such as material loss and all have obvious advantage, be applicable to preparation esterification and prepare polycarboxylic acid water reducer intermediate.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
Heated drying air inlet pipe is connect in a bite of reactor, another mouth connects reflux condensate device, by poly glycol monomethyl ether 1000450g, methacrylic acid 77.4g adds reactor, then para benzoquinone 2.7g and tosic acid 10.8g is added, stir, heat up thawing gradually, start after thawing to stir, be warming up to 110 DEG C and start insulation, temperature controls at 110 ~ 135 DEG C, pass into the heated drying air purging reaction system of 90-130 DEG C continuously from heated drying air inlet pipe in reaction process, heated drying air adopts the instrument air dryer of filling chlorinated calcium to process airflow in advance, again through tubulation, coiled pipe, the preheater of the patterns such as chuck adds temperature to 90 ~ 130 DEG C of warm air, the moisture content that the bottom that heated drying air passes into reactor by inlet pipe through nanopore device produces to take reaction out of, discharge finally by reflux condensate device, after insulation reaction 6-10 hour, cool to 40-50 DEG C of discharging, obtain polyethylene glycol monomethyl ethermethacrylic acid esters or monomethyl polyethylene glycol acrylate ester, recording esterification yield is 98.90%.
Embodiment 2
Heated drying air inlet pipe is connect in a bite of reactor, another mouth connects reflux condensate device, by poly glycol monomethyl ether 1200600g, vinylformic acid 108g adds reactor, then Resorcinol 5.9g and the vitriol oil 22.1 is added, stir, heat up thawing gradually, start after thawing to stir, be warming up to 110 DEG C and start insulation, temperature controls at 110 ~ 135 DEG C, be incubated the intake valve beating heated drying air inlet pipe after two hours, pass into the heated drying air of 90-130 DEG C, the time of passing into is 5-10 minute, every 0.5h operation once, heated drying air adopts the method for swollen evaporation of being splashed again by air compressing post liquefaction to obtain, again through tubulation, coiled pipe, the preheater of the patterns such as chuck adds temperature to 90 ~ 130 DEG C of warm air, the moisture content that heated drying air passes into reactor again bottom through nanopore device produces to take reaction out of, discharge finally by reflux condensate device, after insulation reaction 6-10 hour, cool to 40-50 DEG C of discharging, obtain monomethyl polyethylene glycol acrylate ester, recording esterification yield is 99.36%.
Embodiment 3
Heated drying air inlet pipe is connect in a bite of reactor, another mouth connects reflux condensate device, by poly glycol monomethyl ether 20001000g, methacrylic acid 144g adds reactor, then thiophene piperazine 12g and Sulphanilic Acid 48.1g is added, stir, heat up thawing gradually, start after thawing to stir, be warming up to 110 DEG C and start insulation, temperature controls at 110 ~ 135 DEG C, be incubated the intake valve beating heated drying air inlet pipe after two hours, pass into the heated drying air of 90-130 DEG C, the time of passing into is 5-10 minute, every 0.5h operation once, heated drying air adopts the instrument air dryer of filling the vitriol oil to process airflow, again through tubulation, coiled pipe, the preheater of the patterns such as chuck adds temperature to 90 ~ 130 DEG C of warm air, the moisture content that heated drying air passes into reactor again bottom through nanopore device produces to take reaction out of, discharge finally by reflux condensate device, after insulation reaction 6-10 hour, cool to 40-50 DEG C of discharging, obtain polyethylene glycol monomethyl ethermethacrylic acid esters or monomethyl polyethylene glycol acrylate ester, recording esterification yield is 99.45%.
The above; be only the specific embodiment of the present invention; but protection scope of the present invention is not limited thereto; any those of ordinary skill in the art are in the technical scope disclosed by the present invention; the change can expected without creative work or replacement, all should be encompassed within protection scope of the present invention.Therefore, the protection domain that protection scope of the present invention should limit with claims is as the criterion.
Claims (1)
1. esterification process when preparing polycarboxylate water-reducer, with poly glycol monomethyl ether, methacrylic acid or vinylformic acid are raw material, it is characterized in that: connect heated drying air inlet pipe in a bite of reactor, another mouth connects reflux condensate device, described raw material is added reactor, then stopper and catalyzer is added, stir, heat up thawing gradually, start after thawing to stir, be warming up to 110 DEG C and start insulation, temperature controls at 110 ~ 135 DEG C, the moisture content that the heated drying air simultaneously passing into 90-130 DEG C through nanopore device in the bottom of reactor produces to take reaction out of, discharge finally by reflux condensate device, after insulation reaction 6-10 hour, cool to 40-50 DEG C of discharging, obtain polyethylene glycol monomethyl ethermethacrylic acid esters or monomethyl polyethylene glycol acrylate ester, described heated drying air be by drying treatment after air will through tubulation before passing into esterification system, the preheater of coiled pipe or chuck pattern adds the temperature of warm air to 90-130 DEG C.
2. a kind of esterification process when preparing polycarboxylate water-reducer according to claim 1, is characterized in that: described poly glycol monomethyl ether molecular weight is 1000-2000.
3. a kind of esterification process when preparing polycarboxylate water-reducer according to claim 1, is characterized in that: described poly glycol monomethyl ether and methacrylic acid or acrylic acid mol ratio are 1:2-4.
4. a kind of esterification process when preparing polycarboxylate water-reducer according to claim 1, it is characterized in that: described stopper is Resorcinol, para benzoquinone, one or more mixing in MEHQ or thiophene piperazine, total incorporation accounts for the 0.5%-1.0% of reactant total mass.
5. a kind of esterification process when preparing polycarboxylate water-reducer according to claim 1, it is characterized in that: described esterifying catalyst is one or more mixing in the vitriol oil, tosic acid, Sulphanilic Acid, and total incorporation accounts for the 2%-4% of reactant total mass.
6. a kind of esterification process when preparing polycarboxylate water-reducer according to claim 1, is characterized in that: the air after described drying treatment adopts desiccant-filled instrument air dryer to the obtained dry air of the method processing airflow or air compressing post liquefaction reflation evaporated.
7. a kind of esterification process when preparing polycarboxylate water-reducer according to claim 6, is characterized in that: described siccative is the one in calcium chloride, Bibulous Silica Gel, sodium hydroxide, potassium hydroxide, active oxidation lithium, the vitriol oil or strong phosphoric acid.
8. a kind of esterification process when preparing polycarboxylate water-reducer according to claim 1, is characterized in that: the mode that described heated drying air passes into for continuously or interval purge reaction system.
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| CN111333367A (en) * | 2020-05-18 | 2020-06-26 | 湖南凝英新材料科技有限公司 | Preparation method of polycarboxylate superplasticizer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101117381A (en) * | 2007-07-24 | 2008-02-06 | 王伟松 | Method for synthesizing polyethylene glycol monomethyl ethermethacrylic acid esters by nitrogen with water |
| CN101961640A (en) * | 2010-10-12 | 2011-02-02 | 南京工业大学 | Modified silica gel air drying agent and preparation method thereof |
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| CN101531747B (en) * | 2009-04-20 | 2011-04-20 | 安徽中铁工程材料科技有限公司 | Preparation method of polycarboxylic acids high efficiency water reducer |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101117381A (en) * | 2007-07-24 | 2008-02-06 | 王伟松 | Method for synthesizing polyethylene glycol monomethyl ethermethacrylic acid esters by nitrogen with water |
| CN101961640A (en) * | 2010-10-12 | 2011-02-02 | 南京工业大学 | Modified silica gel air drying agent and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| "空气预热器的设计改进";洪放;《硫酸工业》;20071231(第4期);18-22 * |
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Denomination of invention: Esterification method in preparing polycarboxylate water reducer Effective date of registration: 20191126 Granted publication date: 20150401 Pledgee: Changzhou Institute of building science group Limited by Share Ltd Pledgor: Jiangsu Nigao Technology Co., Ltd. Registration number: Y2019980000719 |
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