CN103382092B - A kind of preparation method of naphthalene water reducer - Google Patents
A kind of preparation method of naphthalene water reducer Download PDFInfo
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- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 42
- DGVVJWXRCWCCOD-UHFFFAOYSA-N naphthalene;hydrate Chemical compound O.C1=CC=CC2=CC=CC=C21 DGVVJWXRCWCCOD-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 62
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 36
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 36
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 30
- 230000007062 hydrolysis Effects 0.000 claims abstract description 20
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 18
- 238000006482 condensation reaction Methods 0.000 claims abstract description 14
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 9
- 238000009833 condensation Methods 0.000 claims abstract description 9
- 230000005494 condensation Effects 0.000 claims abstract description 9
- 239000006227 byproduct Substances 0.000 claims abstract description 3
- 239000012467 final product Substances 0.000 claims abstract description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 97
- 238000006243 chemical reaction Methods 0.000 claims description 66
- 230000035484 reaction time Effects 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 26
- 239000000047 product Substances 0.000 abstract description 17
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000006386 neutralization reaction Methods 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 39
- 235000019256 formaldehyde Nutrition 0.000 description 25
- 239000004568 cement Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 17
- 239000008098 formaldehyde solution Substances 0.000 description 15
- 238000001816 cooling Methods 0.000 description 13
- 238000009413 insulation Methods 0.000 description 13
- 239000007788 liquid Substances 0.000 description 13
- 235000011121 sodium hydroxide Nutrition 0.000 description 13
- 239000004567 concrete Substances 0.000 description 6
- 239000000376 reactant Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical compound C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000004566 building material Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- -1 sulfonate ion Chemical class 0.000 description 1
- 239000008030 superplasticizer Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- Phenolic Resins Or Amino Resins (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a kind of preparation method of naphthalene water reducer, comprise the following steps: sulfonation: naphthalene and vitriol oil generation sulfonation reaction; Hydrolysis: add water in sulfonation reaction product generation hydrolysis reaction, by product in hydrolysis sulfonation reaction; Condensation: add paraformaldehyde and water generation condensation reaction in hydrolysis reaction product; Neutralization: condensation reaction products adjusts pH6-8, dry, to obtain final product.This preparation method's production technique simple and stable, parameter are easily controlled, and obtained naphthalene water reducer product performance are stable, quality is good.
Description
Technical field
The invention belongs to building material field, relate to a kind of preparation method of chemical admixture, be specifically related to a kind of preparation method of naphthalene water reducer.
Background technology
Cement water reducing agent is under concrete workability and cement consumption permanence condition, can reduce mixing water amount, improve concrete strength, save the admixture of cement consumption.Naphthalene water reducer is maximum, the most widely used a kind of high efficiency water reducing agent of usage quantity on domestic market.According to statistics, naphthalene systems in 2009 etc. two generation water reducer accounts for all synthesis water reducer ultimate productions 67.5%, within 2010, be 67.1%, within 2011, be 66.5%, although proportion declines year by year, its price is relatively cheap, and good with hardening accelerator, retardant compound property, multi-functional composite superplasticizer can be formed, commercially still widely use at present.
After naphthalene water reducer mixes concrete, be adsorbed on the surface of cement, cement particle surface is adsorbed a large amount of sulfonate ion, thus make cement granules electronegative, mutual repulsion between negative charge makes cement scatter, thus water consumption when effectively can reduce mix.In addition, add the hydration process that naphthalene water reducer can also improve cement, promote the growth of mineral crystal, improve the pore structure of Behavior of Hardened Cement Paste, improve concrete density.
The preparation method of current naphthalene water reducer obtains product through drying after mainly comprising the reactions such as sulfonation, hydrolysis, condensation, neutralization, and its synthesis material mainly contains NAPTHALENE FLAKES. (INDUSTRIAL GRADE）, the vitriol oil, formaldehyde and alkali.The sulfonated products of naphthalene has α-naphthalenesulfonicacid, beta-naphthalenesulfonic-acid and many sulfonated products, but wherein only can have beta-naphthalenesulfonic-acid with the effective condensation composition of formaldehyde.Wherein, in conventional preparation techniques, the condensation reaction stage generally adopts and drops in the system after hydrolysis reaction by 37% formalin, drips process control between 1.5 ~ 3.0h.But in reactor, temperature is generally 80 ~ 100 DEG C during condensation reaction, formaldehyde is added drop-wise in reactor and is easy to volatilization, formaldehyde therefore can be caused to measure inaccurate.Patent CN101270066 provides a kind of way of reducing methanal attrition in process of preparing naphthalin series water reducing agent, the line end water seal specifically will be communicated with reactor, the formaldehyde in all right recycle-water.Although this method can solve the problem of formaldehyde volatilization, be the increase in equipment and production cost.In addition, in the winter time, the longer easy precipitation white solid of formaldehyde solution waiting time, what formaldehyde can be caused equally to measure is inaccurate.Formaldehyde measures inaccurate meeting and causes condensation reaction uncontrollable, and then makes product performance produce fluctuation.
Summary of the invention
Goal of the invention: the preparation method that the object of this invention is to provide a kind of stable processing technique, naphthalene water reducer that product performance are stable.
Technical scheme: the preparation method of a kind of naphthalene water reducer provided by the invention, is characterized in that: comprise the following steps:
(1) sulfonation: naphthalene and vitriol oil generation sulfonation reaction;
(2) be hydrolyzed: add water in sulfonation reaction product generation hydrolysis reaction, by product in hydrolysis sulfonation reaction;
(3) condensation: add paraformaldehyde and water generation condensation reaction in hydrolysis reaction product;
(4) neutralize: condensation reaction products adjusts pH6-8, dry, to obtain final product.
Wherein, in step (1), the purity of naphthalene is more than 95%, and the mass percent concentration of the vitriol oil is more than 98%; The mol ratio of naphthalene and the vitriol oil is 1:(1.30 ~ 1.50), sulfonation reaction temperature is 150 ~ 175 DEG C, and the sulfonation reaction time is 1.5 ~ 4.0h; Temperature of reaction lower than 150 DEG C, the reaction times is less than 1.5h, the transformation efficiency of naphthalene is on the low side, beta-naphthalenesulfonic-acid content is on the low side in sulfonated products, can cause naphthalene water reducer degradation; Temperature higher than 175 DEG C, sulfonation time more than 4.0h, in sulfonated products, many sulfonated products are on the high side, and the easy carbonization of reactant, thus cause water reducer degradation.
Wherein, in step (2), hydrolysising reacting temperature is 100 ~ 120 DEG C, and hydrolysis time is 0.5 ~ 1.5h; By regulating the acidity of the rear reaction system of amount of water controlled hydrolysis reaction in hydrolysis reaction to be 26 ~ 30%; Acidity can cause the condensation reaction rate of lower step slow lower than 26%, long reaction time, and production efficiency reduces; Acidity can cause the condensation reaction rate of lower step too fast higher than 30%, and quick heating, product performance reduce.
Wherein, in step (3), the molecular formula of described paraformaldehyde is (CH
2o) n, wherein n=8 ~ 100; The mol ratio of paraformaldehyde and naphthalene is 0.9 ~ 1.5, and the molar weight of paraformaldehyde is in formaldehyde; Wherein, paraformaldehyde is converted to the method for formaldehyde and is: n
formaldehyde=m/30, wherein n
formaldehydefor converting the mole number of rear formaldehyde, the quality of unit to be mol, m be paraformaldehyde, unit to be g, n be 8 ~ 100 natural number.The mass ratio of paraformaldehyde and water is 1:(1 ~ 3), if directly add paraformaldehyde and do not add water and carry out condensation, after paraformaldehyde resolves into formaldehyde, the too high initial condensation speed of reaction that makes of concentration of formaldehyde is too fast, this may cause heating up too fast thus reducing the performance of water reducer, therefore need to add with paraformaldehyde 1 ~ 3 times of quality water control to be polymerized the speed at initial stage.Setting-up point is 100 ~ 120 DEG C, and condensation reaction time is 2 ~ 8h.After adding paraformaldehyde and water, along with the carrying out of reaction, reaction viscosity also can increase, and therefore, should add hot water dilute reaction solution in condensation reaction, thus reduces reactant viscosity, keeps temperature of reaction constant.
Beneficial effect: preparation method's production technique simple and stable of naphthalene water reducer provided by the invention, parameter are easily controlled, obtained naphthalene water reducer product performance are stable, quality is good.
Specifically, the present invention adds paraformaldehyde and carries out condensation in condensation step, has following outstanding advantage compared to traditional technology:
(1) cost is low, efficiency is high: traditional technology drips the formaldehyde solution of about 37%, 1.5 ~ 3h consuming time, and the present invention adopts paraformaldehyde to drop into reaction kettle for reaction, and production technique is simple, substantially increases production efficiency, also reduces transport, Holding Cost simultaneously;
(2) product performance are high: because paraformaldehyde is solid, when dropping into reaction kettle for reaction, paraformaldehyde mainly dissolves-decomposes-process of reacting, by the Co ntrolled release of effective PARA FORMALDEHYDE PRILLS(91,95) molecule, thus make speed of reaction steadily, evenly, therefore effectively can increase the polymerization degree of naphthalene water reducer, thus substantially increase the performance of water reducer;
(3) product performance are stablized: by the formaldehyde solution of about 37% in traditional technology, the time long or low meeting of temperature causes crystallize out, not only cause formaldehyde effective content in formaldehyde solution to reduce, even can blocking pipe; Be added drop-wise in reaction solution in formaldehyde solution, due to temperature 80 ~ 100 DEG C, in dropping process formaldehyde some can vapor away; Above factor all can make the metering of formaldehyde inaccurate, thus causes the product performance of producing to there is fluctuation.The present invention adopts the paraformaldehyde of solid as reactant, and its metering is simple, accurate, there is the process of dissolving-decomposition-reaction, not easily volatilize formaldehyde molecule after adding, and therefore makes the product performance of production more stable.
Embodiment
According to following embodiment, the present invention may be better understood.But those skilled in the art will readily understand, concrete material proportion, processing condition and result thereof described by embodiment only for illustration of the present invention, and should can not limit the present invention described in detail in claims yet.In embodiment, raw materials used all purchase by business is obtained.
Embodiment 1
134.7g NAPTHALENE FLAKES. (INDUSTRIAL GRADE） (purity >=95%, 1.0mol) is added, the 140.0g vitriol oil (purity >=98% in reaction flask, 1.4mol), be warmed up to 165 ~ 170 DEG C of reaction 2h, after reaction terminates, add a certain amount of water, be hydrolyzed 0.5h at 110 DEG C, after hydrolysis, Controlled acidity is 28%.After cooling to 90 DEG C, add 34.4g paraformaldehyde (purity >=96%, 1.1mol is in formaldehyde) and 58.5g water, be warmed up to 100 ~ 105 DEG C gradually, insulation 4h, adds water management and is polymerized under suitable viscosity in insulating process.Add liquid caustic soda after reaction terminates and regulate pH=6 ~ 8, dry, obtain naphthalene water reducer.
Embodiment 2
134.7g NAPTHALENE FLAKES. (INDUSTRIAL GRADE） (purity >=95%, 1.0mol) is added, the 130.0g vitriol oil (purity >=98% in reaction flask, 1.3mol), be warmed up to 150 ~ 155 DEG C of reaction 4h, after reaction terminates, add a certain amount of water, be hydrolyzed 1.5h at 100 DEG C, after hydrolysis, Controlled acidity is 26%.After cooling to 80 DEG C, add 27.0g paraformaldehyde (purity >=99%, 0.9mol is in formaldehyde) and 54.0g water, be warmed up to 100 ~ 105 DEG C gradually, insulation 8h, adds water management and is polymerized under suitable viscosity in insulating process.Add liquid caustic soda after reaction terminates and regulate pH=6 ~ 8, dry, obtain naphthalene water reducer.
Embodiment 3
134.7g NAPTHALENE FLAKES. (INDUSTRIAL GRADE） (purity >=95%, 1.0mol) is added, the 135.0g vitriol oil (purity >=98% in reaction flask, 1.35mol), be warmed up to 170 ~ 175 DEG C of reaction 1.5h, after reaction terminates, add a certain amount of water, be hydrolyzed 0.5h at 120 DEG C, after hydrolysis, Controlled acidity is 26%.After cooling to 90 DEG C, add 40.6g paraformaldehyde (purity >=96%, 1.3mol is in formaldehyde) and 40.6g water, be warmed up to 115 ~ 120 DEG C gradually, insulation 8h, adds water management and is polymerized under suitable viscosity in insulating process.Add liquid caustic soda after reaction terminates and regulate pH=6 ~ 8, dry, obtain naphthalene water reducer.
Embodiment 4
134.7g NAPTHALENE FLAKES. (INDUSTRIAL GRADE） (purity >=95%, 1.0mol) is added, the 150.0g vitriol oil (purity >=98% in reaction flask, 1.50mol), be warmed up to 165 ~ 170 DEG C of reaction 1.5h, after reaction terminates, add a certain amount of water, be hydrolyzed 0.5h at 110 DEG C, after hydrolysis, Controlled acidity is 30%.After cooling to 100 DEG C, add 46.9g paraformaldehyde (purity >=96%, 1.5mol is in formaldehyde) and 140.7g water, be warmed up to 105 ~ 110 DEG C gradually, insulation 2h, adds water management and is polymerized under suitable viscosity in insulating process.Add liquid caustic soda after reaction terminates and regulate pH=6 ~ 8, dry, obtain naphthalene water reducer.
Embodiment 5
134.7g NAPTHALENE FLAKES. (INDUSTRIAL GRADE） (purity >=95%, 1.0mol) is added, the 145.0g vitriol oil (purity >=98% in reaction flask, 1.45mol), be warmed up to 165 ~ 170 DEG C of reaction 2h, after reaction terminates, add a certain amount of water, be hydrolyzed 0.5h at 110 DEG C, after hydrolysis, Controlled acidity is 29%.After cooling to 90 DEG C, add 34.4g paraformaldehyde (purity >=96%, 1.1mol is in formaldehyde) and 68.8g water, be warmed up to 100 ~ 105 DEG C gradually, insulation 4h, adds water management and is polymerized under suitable viscosity in insulating process.Add liquid caustic soda after reaction terminates and regulate pH=6 ~ 8, dry, obtain naphthalene water reducer.
Embodiment 6
134.7g NAPTHALENE FLAKES. (INDUSTRIAL GRADE） (purity >=95%, 1.0mol) is added, the 140.0g vitriol oil (purity >=98% in reaction flask, 1.4mol), be warmed up to 165 ~ 170 DEG C of reaction 2h, after reaction terminates, add a certain amount of water, be hydrolyzed 0.5h at 110 DEG C, after hydrolysis, Controlled acidity is 28%.After cooling to 90 DEG C, add 31.3g paraformaldehyde (purity >=96%, 1.0mol is in formaldehyde) and 58.5g water, be warmed up to 100 ~ 105 DEG C gradually, insulation 4h, adds water management and is polymerized under suitable viscosity in insulating process.Add liquid caustic soda after reaction terminates and regulate pH=6 ~ 8, dry, obtain naphthalene water reducer.
Embodiment 7
134.7g NAPTHALENE FLAKES. (INDUSTRIAL GRADE） (purity >=95%, 1.0mol) is added, the 140.0g vitriol oil (purity >=98% in reaction flask, 1.4mol), be warmed up to 165 ~ 170 DEG C of reaction 2h, after reaction terminates, add a certain amount of water, be hydrolyzed 0.5h at 110 DEG C, after hydrolysis, Controlled acidity is 28%.After cooling to 90 DEG C, add 34.4g paraformaldehyde (purity >=96%, 1.1mol is in formaldehyde) and 58.5g water, be warmed up to 100 ~ 105 DEG C gradually, insulation 5h, adds water management and is polymerized under suitable viscosity in insulating process.Add liquid caustic soda after reaction terminates and regulate pH=6 ~ 8, dry, obtain naphthalene water reducer.
Embodiment 8
134.7g NAPTHALENE FLAKES. (INDUSTRIAL GRADE） (purity >=95%, 1.0mol) is added, the 140.0g vitriol oil (purity >=98% in reaction flask, 1.4mol), be warmed up to 165 ~ 170 DEG C of reaction 2h, after reaction terminates, add a certain amount of water, be hydrolyzed 0.5h at 110 DEG C, after hydrolysis, Controlled acidity is 28%.After cooling to 95 DEG C, add 34.4g paraformaldehyde (purity >=96%, 1.1mol is in formaldehyde) and 86.0g water, be warmed up to 100 ~ 105 DEG C gradually, insulation 4h, adds water management and is polymerized under suitable viscosity in insulating process.Add liquid caustic soda after reaction terminates and regulate pH=6 ~ 8, dry, obtain naphthalene water reducer.
Comparative example 1
This comparative example is for embodiment 1, replace by 37% formaldehyde solution that paraformaldehyde is disposable joins in reactor: in reaction flask, add 134.7g NAPTHALENE FLAKES. (INDUSTRIAL GRADE） (purity >=95%, 1.0mol), the 140.0g vitriol oil (purity >=98%, 1.4mol), be warmed up to 165 ~ 170 DEG C of reaction 2h, after reaction terminates, add a certain amount of water, be hydrolyzed 0.5h at 110 DEG C, after hydrolysis, Controlled acidity is 28%.After cooling to 90 DEG C, disposablely add 89.2g formaldehyde solution (37%, 1.1mol), be warmed up to 100 ~ 105 DEG C gradually, insulation 4h, adds water management and is polymerized under suitable viscosity in insulating process.Adding liquid caustic soda after reaction terminates regulates pH=6 ~ 8 to obtain naphthalene water reducer.
Comparative example 2
This comparative example is for embodiment 1, replace paraformaldehyde by 37% formaldehyde solution and be added drop-wise in 1h in reaction flask: in reactor, adding 134.7g NAPTHALENE FLAKES. (INDUSTRIAL GRADE） (purity >=95%, 1.0mol), the 140.0g vitriol oil (purity >=98%, 1.4mol), be warmed up to 165 ~ 170 DEG C of reaction 2h, after reaction terminates, add a certain amount of water, be hydrolyzed 0.5h at 110 DEG C, after hydrolysis, Controlled acidity is 28%.After cooling to 90 DEG C, be added dropwise to 89.2g formaldehyde solution (37%, 1.1mol), be warmed up to 100 ~ 105 DEG C gradually in 2h, insulation 4h, adds water management and is polymerized under suitable viscosity in insulating process.Adding liquid caustic soda after reaction terminates regulates pH=6 ~ 8 to obtain naphthalene water reducer.
Comparative example 3
This comparative example is for embodiment 1, replace paraformaldehyde by 37% formaldehyde solution and be added drop-wise in 2h in reaction flask: in reactor, adding 134.7g NAPTHALENE FLAKES. (INDUSTRIAL GRADE） (purity >=95%, 1.0mol), the 140.0g vitriol oil (purity >=98%, 1.4mol), be warmed up to 165 ~ 170 DEG C of reaction 2h, after reaction terminates, add a certain amount of water, be hydrolyzed 0.5h at 110 DEG C, after hydrolysis, Controlled acidity is 28%.After cooling to 90 DEG C, be added dropwise to 89.2g formaldehyde solution (37%, 1.1mol), be warmed up to 100 ~ 105 DEG C gradually in 2h, insulation 4h, adds water management and is polymerized under suitable viscosity in insulating process.Adding liquid caustic soda after reaction terminates regulates pH=6 ~ 8 to obtain naphthalene water reducer.
Comparative example 4
This comparative example is for embodiment 1, replace paraformaldehyde by 37% formaldehyde solution and be added drop-wise in 3h in reaction flask: in reactor, adding 134.7g NAPTHALENE FLAKES. (INDUSTRIAL GRADE） (purity >=95%, 1.0mol), the 140.0g vitriol oil (purity >=98%, 1.4mol), be warmed up to 165 ~ 170 DEG C of reaction 2h, after reaction terminates, add a certain amount of water, be hydrolyzed 0.5h at 110 DEG C, after hydrolysis, Controlled acidity is 28%.After cooling to 90 DEG C, be added dropwise to 89.2g formaldehyde solution (37%, 1.1mol), be warmed up to 100 ~ 105 DEG C gradually in 2h, insulation 4h, adds water management and is polymerized under suitable viscosity in insulating process.Adding liquid caustic soda after reaction terminates regulates pH=6 ~ 8 to obtain naphthalene water reducer.
Comparative example 5
Naphthalene system processing parameter synthesis (" New Building Materials " the 3rd phase 27-29 page in 2004) that this comparative example is optimized according to Li Qiuyi etc.: add 134.7g NAPTHALENE FLAKES. (INDUSTRIAL GRADE） (purity >=95% in reactor, 1.0mol), the 136.0g vitriol oil (purity >=98%, 1.36mol), be warmed up to 161 ~ 165 DEG C of reaction 2.5h, add a certain amount of water after reaction terminates, be hydrolyzed 0.5h at 130 DEG C, after hydrolysis, acidity is 28%.After cooling to 95 DEG C, be added dropwise to 81.1g formaldehyde solution (37%, 1.0mol), be warmed up to 100 ~ 105 DEG C gradually in 2h, insulation 3h, adds water management and is polymerized under suitable viscosity in insulating process.Adding liquid caustic soda after reaction terminates regulates pH=6 ~ 8 to obtain naphthalene water reducer.
Measure the flowing degree of net paste of cement of naphthalene water reducer
Reference standard GB/T8077-2000 " Methods for testing uniformity of concrete admixture " has carried out flowing degree of net paste of cement test, cement (little wild field 52.5R.P. II) 300g, amount of water is 87g, stirs and on sheet glass, measures flowing degree of net paste of cement after 3 minutes, the results are shown in Table 1.
The flowing degree of net paste of cement of the naphthalene water reducer that table 1 embodiment and comparative example obtain
| Sample | Volume | Flowing degree of net paste of cement/mm |
| Embodiment 1 | 0.4% | 255 |
| Embodiment 2 | 0.4% | 257 |
| Embodiment 3 | 0.4% | 257 |
| Embodiment 4 | 0.4% | 255 |
| Embodiment 5 | 0.4% | 250 |
| Embodiment 6 | 0.4% | 255 |
| Embodiment 7 | 0.4% | 253 |
| Embodiment 8 | 0.4% | 252 |
| Comparative example 1 | 0.4% | 222 |
| Comparative example 2 | 0.4% | 225 |
| Comparative example 3 | 0.4% | 227 |
| Comparative example 4 | 0.4% | 226 |
| Comparative example 5 | 0.4% | 227 |
Wherein, in table 1, volume is that water reducer is converted to the ratio of solid compared to the consumption of 300g cement.
As can be seen from embodiment 1 ~ 8, paraformaldehyde is adopted to synthesize as reactant the naphthalene water reducer performance obtained higher, and steady quality.Comparative example 1 ~ 5 adopts traditional formaldehyde solution to make condensing agent, and the product obtained is dispersed lower than the product making reactant of paraformaldehyde to the dispersiveness of cement.
Claims (2)
1. a preparation method for naphthalene water reducer, is characterized in that: comprise the following steps:
(1) sulfonation: naphthalene and vitriol oil generation sulfonation reaction; The mol ratio of naphthalene and the vitriol oil is 1:(1.30 ~ 1.50); Sulfonation reaction temperature is 150 ~ 175 DEG C, and the sulfonation reaction time is 1.5 ~ 4.0;
(2) be hydrolyzed: add water in sulfonation reaction product generation hydrolysis reaction, by product in hydrolysis sulfonation reaction; By regulating the acidity of the rear reaction system of amount of water controlled hydrolysis reaction to be 26 ~ 30%; Hydrolysising reacting temperature is 100 ~ 120 DEG C, and hydrolysis time is 0.5 ~ 1.5h;
(3) condensation: add paraformaldehyde and water generation condensation reaction in hydrolysis reaction product; The mol ratio of paraformaldehyde and naphthalene is 0.9 ~ 1.5, and the molar weight of paraformaldehyde is in formaldehyde; The mass ratio of paraformaldehyde and water is 1:(1 ~ 3), setting-up point is 100 ~ 120 DEG C, and condensation reaction time is 2 ~ 8h;
(4) neutralize: condensation reaction products adjusts pH6-8, dry, to obtain final product.
2. the preparation method of a kind of naphthalene water reducer according to claim 1, is characterized in that: in step (1), and the purity of naphthalene is more than 95%, and the mass percent concentration of the vitriol oil is more than 98%.
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| CN105294967B (en) * | 2015-10-20 | 2017-10-10 | 江苏苏博特新材料股份有限公司 | A kind of anti-stick soil type naphthalene water reducer and preparation method thereof |
| CN105271887B (en) * | 2015-10-20 | 2017-10-10 | 江苏苏博特新材料股份有限公司 | A kind of collapse protection type modified naphthalene series water-reducing agent and preparation method thereof |
| CN105293973B (en) * | 2015-10-27 | 2017-11-28 | 中国建筑材料科学研究总院 | Naphthalene series high-efficiency water-reducing agent and preparation method thereof |
| CN106632930B (en) * | 2016-09-18 | 2019-03-08 | 江苏苏博特新材料股份有限公司 | A kind of modified condensation polymer type water-reducing agent, preparation method and its application |
| CN106632938B (en) * | 2016-09-20 | 2019-01-01 | 江苏苏博特新材料股份有限公司 | A kind of energy saving preparation method and its special equipment of naphthalene water reducer |
| CN110357796A (en) * | 2019-07-03 | 2019-10-22 | 山东万山集团有限公司 | The preparation method of continuous extraction process and extractant, naphthalene sulfonic acids and water-reducing agent |
| CN113121771B (en) * | 2019-12-30 | 2022-12-02 | 江苏苏博特新材料股份有限公司 | Air-entraining modified naphthalene water reducer and preparation method thereof |
| CN111470793B (en) * | 2020-05-12 | 2022-03-04 | 广东柯杰科技实业有限公司 | High-dispersity high-quality naphthalene-based high-efficiency water reducing agent and preparation method thereof |
| CN114106893A (en) * | 2021-12-24 | 2022-03-01 | 莱芜市兆信新材料股份有限公司 | Preparation method of naphthalene water reducer for coal water slurry |
| CN114230492B (en) * | 2021-12-29 | 2023-07-21 | 山西永红建材化工有限公司 | Preparation process of concrete modified additive |
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| CN101723860B (en) * | 2009-12-08 | 2013-04-24 | 上虞吉龙化学建材有限公司 | Method for preparing naphthalene series water reducing agent |
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| 以工业萘和粗甲基萘为主要原料合成萘系高效减水剂;胡相红等;《化学研究与应用》;20010831;第13卷(第4期);465-467 * |
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