CN106186781B - A kind of preparation method of modified naphthalene series water-reducing agent - Google Patents
A kind of preparation method of modified naphthalene series water-reducing agent Download PDFInfo
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- CN106186781B CN106186781B CN201610498001.2A CN201610498001A CN106186781B CN 106186781 B CN106186781 B CN 106186781B CN 201610498001 A CN201610498001 A CN 201610498001A CN 106186781 B CN106186781 B CN 106186781B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/20—Sulfonated aromatic compounds
- C04B24/22—Condensation or polymerisation products thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
- C08F8/36—Sulfonation; Sulfation
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
Abstract
The present invention relates to a kind of preparation methods of modified naphthalene series water-reducing agent, belong to concrete admixture field, preparation method includes the following steps：(1) unsaturated dicarboxylic acid, styrene and acrylic acid hydroxy alkyl ester are used, cocondensation polycondensation monomer is made under sodium hypophosphite and initiator effect；(2) use homologue, cocondensation polycondensation monomer, the concentrated sulfuric acid, phosphoric acid and the formaldehyde etc. of naphthalene, sulfonated, hydrolysis, condensation and neutralization four-stage that modified naphthalene series water-reducing agent is made.The present invention introduces a large amount of carboxyl, hydroxyl and phosphate in the molecular structure of water-reducing agent, while keeping naphthalene water reducer high water reducing rate, the aquation of cement can be delayed, then improving the slump-retaining of concrete can, it is allowed to also have higher fluidity after 2h, is readily transported and constructs；Preparation process of the present invention is simple, easy to use, effect is good, highly practical.
Description
Technical field
The invention belongs to the technical field of concrete additives in construction material, and in particular to a kind of modified naphthalene series diminishing
Agent, the more particularly to preparation method of this kind water-reducing agent.
Background technology
Water-reducing agent is also known as plasticiser, is one of the additive for improving rheological property of concrete, has been increasingly becoming modern mixed
The 5th component in solidifying soil in addition to cement, sand, stone and water.
Common water-reducing agent can be divided into lignin sulfonic acid system, naphthalene system, melamine series, amido sulfoacid series and poly- carboxylic by kind
Acid system etc. can be divided into ordinary water-reducing agent, high efficiency water reducing agent and high-performance water reducing agent by water-reducing rate height.The thirties in last century is to 60
Age is application and the developing period of ordinary water-reducing agent, and predominantly sodium abietate, sodium lignin sulfonate, odium stearate etc. organises
Object is closed, main function is the application property for improving concrete, solves the endurance issues such as the freeze thawing resistance of concrete road surface.However,
With the continuous improvement of construction requirement, the water-reducing effect of these early stage water-reducing agents cannot meet the need of modern construction
It wants.
The take portion Japanese from 1962 strong one develops naphthalenesulfonate formaldehyde condensation compound high efficiency water reducing agent first, and (i.e. naphthalene system subtracts
Aqua) since, exploitation and the application period of high efficiency water reducing agent are entered, the development of concrete technology has effectively been pushed.As
The outstanding feature of the representative of second generation water-reducing agent, naphthalene water reducer is that water-reducing rate is high, cement dispersion effect is good, can be greatly lowered
Folk prescription water consumption or single cement consumption, for preparing high-strength, high durability concrete, but the disadvantage is that slump-loss compared with
Greatly, constructional difficulties are caused, and along with high performance concrete to the water-reducing property, dispersion performance and slump of high efficiency water reducing agent
What degree retention property required further increases, and people more and more pay attention to the synthesis modification of naphthalene water reducer and the research of compounding.
Invention content
The present invention is directed to overcome above-mentioned deficiency in the prior art, provide that a kind of water-reducing rate is high, slump retaining is good, cost-effective
Modified naphthalene series water-reducing agent preparation method.
A kind of preparation method of modified naphthalene series water-reducing agent, which is characterized in that include the following steps：
(1) preparation of cocondensation polycondensation monomer：
A certain amount of water, unsaturated dicarboxylic acid, styrene and sodium hypophosphite are put into a kettle, under constant stirring
It is heated to 60~70 DEG C；It is 5~7 that 32% liquid caustic soda, which is added, and adjusts the pH value of reaction system；Acrylic acid hydroxy alkyl ester, initiator is added dropwise
Add the mixed solution that water is made into, control rate of addition drips off in 2~4h, and continues 2~4h of heat preservation at 60~70 DEG C；Stop adding
Heat is cooled to 40 DEG C or so dischargings to get cocondensation polycondensation monomer.
(2) preparation of modified naphthalene series water-reducing agent：
(1) sulfonation：The homologue of naphthalene is put into reaction kettle and heating is melted to 130~135 DEG C, and 98% concentrated sulfuric acid is added,
In 150~170 DEG C of 3~4h of sulfonating reaction, sulfonation material is obtained；
(2) it hydrolyzes：100~130 DEG C are cooled to, a certain amount of phosphoric acid and water is added, hydrolyzes 1~2h；
(3) it is condensed：Material through hydrolysing step is cooled to 90~105 DEG C, and cocondensation polycondensation monomer is added, adds formaldehyde,
100~105 DEG C carry out 3~4h of condensation reaction；
(4) it neutralizes：Aforementioned condensation material, which is transferred to, to be neutralized kettle and 32% liquid caustic soda and water is added, and it is 8 that reactant, which is neutralized to pH value,
~10 to get to the modified naphthalene series water-reducing agent.
The unsaturated dicarboxylic acid is in maleic acid, maleic anhydride, fumaric acid, fumaric acid anhydride, itaconic acid or citraconic acid
One kind.
The acrylic acid hydroxy alkyl ester is one kind in hydroxy-ethyl acrylate or hydroxypropyl acrylate.
The initiator is one or more of persulfuric acid salt, including potassium peroxydisulfate, ammonium persulfate or sodium peroxydisulfate.
The styrene:Unsaturated dicarboxylic acid:The molar ratio of acrylic acid hydroxy alkyl ester is (0.25~0.5):1:(1.0
~1.6), sodium hypophosphite dosage is the 12~20% of monomer gross mass, and initiator amount is the 0.5~2% of monomer gross mass.
The homologue of the naphthalene is the mixture of one or more of crude naphthalene, methyl naphthalene and betanaphthol.
The molar ratio of the homologue of the concentrated sulfuric acid and naphthalene is (1.1~1.8):1.
The phosphoric acid dosage is the 4~12% of concentrated sulfuric acid quality.
The cocondensation polycondensation monomer dosage is 5~10% with the homologue gross mass of naphthalene.
The molar ratio of the homologue of the formaldehyde and naphthalene is (0.8~1.4):1.
Compared with prior art, the present invention has following features and advantageous effect：
The present invention introduces a large amount of carboxyl, hydroxyl and phosphate in the molecular structure of water-reducing agent, is keeping naphthalene system diminishing
While agent high water reducing rate, the aquation of cement can be delayed, then improve the slump-retaining energy of concrete, be allowed to after 2h
Also higher fluidity, is readily transported and constructs.
Preparation process of the present invention is simple, easy to use, effect is good, highly practical.
Specific implementation mode
Below with specific embodiment come the embodiment that the present invention will be described in detail, whereby to the present invention how application technology hand
Section solves technical problem, and the realization process for reaching technique effect can fully understand and implement.
Embodiment 1：
(1) preparation of cocondensation polycondensation monomer：
163.3 parts of fumaric acid, 40.4 parts of styrene, 59.1 parts of sodium hypophosphites and 255.5 parts of water, side are put into a kettle
Stirring side is heated to 60~70 DEG C；It is 5~7 that 65.0 part of 32% liquid caustic soda, which is added, and adjusts the pH value of reaction system；By 210.5 parts of propylene
Sour hydroxyl ethyl ester and 6.2 parts of ammonium persulfates are added in 200 parts of water, are made into mixed liquor, and drip off in 3~4h；Rear constant temperature is added dropwise
React 3~4h；Stop heating, is cooled to 40 DEG C or so dischargings to get cocondensation polycondensation monomer A.
(2) a kind of modified naphthalene series water-reducing agent, preparation process are as follows：
(1) sulfonation：138 parts of crude naphthalenes are put into reaction kettle and 28 parts of methyl naphtho- heating are melted to 130~135 DEG C, are added
Enter 145 part of 98% concentrated sulfuric acid, in 160 DEG C of 3~4h of sulfonating reaction；
(2) it hydrolyzes：120 DEG C are cooled to, 9.7 parts of phosphoric acid and 100 parts of water are added, hydrolyzes 1~2h；
(3) it is condensed：95 DEG C are cooled to, 26.9 parts of cocondensation polycondensation monomer A are added, 95 parts of formaldehyde are then added, 100~105
DEG C carry out condensation reaction 3~4h；
(4) it neutralizes：Aforementioned condensation material, which is transferred to, to be neutralized kettle and 148 part of 32% liquid caustic soda and 233 parts of water is added, and reactant is neutralized
It is 8~10 to get to modified naphthalene series water-reducing agent to pH value.
Embodiment 2：
(1) preparation of cocondensation polycondensation monomer：
148.6 parts of maleic anhydrides, 67.1 parts of styrene, 57.0 parts of sodium hypophosphites and 258.2 parts of water are put into a kettle,
It is heated to 60~70 DEG C while stirring；It is 5~7 that 62.0 part of 32% liquid caustic soda, which is added, and adjusts the pH value of reaction system；By 200.3 part third
Olefin(e) acid hydroxypropyl acrylate and 6.8 parts of ammonium persulfates are added in 200 parts of water, are made into mixed liquor, and drip off in 3~4h；Perseverance after being added dropwise
2~3h of temperature reaction；Stop heating, is cooled to 40 DEG C or so dischargings to get cocondensation polycondensation monomer B.
(2) a kind of modified naphthalene series water-reducing agent, preparation process are as follows：
(1) sulfonation：128 parts of crude naphthalenes and 46 parts of betanaphthols are put into reaction kettle and are heated and are melted to 130~135 DEG C, are added
Enter 150 part of 98% concentrated sulfuric acid, in 160 DEG C of 3~4h of sulfonating reaction；
(2) it hydrolyzes：120 DEG C are cooled to, 10.4 parts of phosphoric acid and 100 parts of water are added, hydrolyzes 1~2h；
(3) it is condensed：95 DEG C are cooled to, 24.4 parts of cocondensation polycondensation monomer B are added, 132 parts of formaldehyde are then added, 100~105
DEG C carry out condensation reaction 3~4h；
(4) it neutralizes：Aforementioned condensation material, which is transferred to, to be neutralized kettle and 142 part of 32% liquid caustic soda and 244 parts of water is added, and reactant is neutralized
It is 8~10 to get to modified naphthalene series water-reducing agent to pH value.
Embodiment 3：
(1) preparation of cocondensation polycondensation monomer：
137.5 parts of citraconic acids, 51.8 parts of styrene, 72.4 parts of sodium hypophosphites and 261.4 parts of water, side are put into a kettle
Stirring side is heated to 60~70 DEG C；It is 5~7 that 56.8 part of 32% liquid caustic soda, which is added, and adjusts the pH value of reaction system；By 212.6 parts of propylene
Sour hydroxypropyl acrylate and 6.3 parts of potassium peroxydisulfates are added in 200 parts of water, are made into mixed liquor, and drip off in 3~4h；Rear constant temperature is added dropwise
React 3~4h；Stop heating, is cooled to 40 DEG C or so dischargings to get cocondensation polycondensation monomer C.
(2) a kind of modified naphthalene series water-reducing agent, preparation process are as follows：
(1) sulfonation：162 parts of industrial naphtho- heating are put into reaction kettle and are melted to 130~135 DEG C, are added 163.7 part 98%
The concentrated sulfuric acid, in 160 DEG C of 3~4h of sulfonating reaction；
(2) it hydrolyzes：120 DEG C are cooled to, 8.2 parts of phosphoric acid and 100 parts of water are added, hydrolyzes 1~2h；
(3) it is condensed：95 DEG C are cooled to, 21.1 parts of cocondensation polycondensation monomer C are added, 118 parts of formaldehyde are then added, 100~105
DEG C carry out condensation reaction 3~4h；
(4) it neutralizes：Aforementioned condensation material, which is transferred to, to be neutralized kettle and 162 part of 32% liquid caustic soda and 240 parts of water is added, and reactant is neutralized
It is 8~10 to get to modified naphthalene series water-reducing agent to pH value.
Embodiment 4：
(1) preparation of cocondensation polycondensation monomer：
149.6 parts of maleic acids, 44.2 parts of styrene, 69.5 parts of sodium hypophosphites and 257.5 parts of water, side are put into a kettle
Stirring side is heated to 60~70 DEG C；It is 5~7 that 27.4 parts of sodium hydroxides, which are added, and adjust the pH value of reaction system；By 209.7 parts of propylene
Sour hydroxypropyl acrylate and 7.1 parts of ammonium persulfates are added in 200 parts of water, are made into mixed liquor, and drip off in 4~5h；Rear constant temperature is added dropwise
React 2~3h；Stop heating, is cooled to 40 DEG C or so dischargings to get cocondensation polycondensation monomer D.
(2) a kind of modified naphthalene series water-reducing agent, preparation process are as follows：
(1) sulfonation：116 parts of crude naphthalenes are put into reaction kettle and 52 parts of methyl naphtho- heating are melted to 130~135 DEG C, are added
Enter 174.5 part of 98% concentrated sulfuric acid, in 160 DEG C of 3~4h of sulfonating reaction；
(2) it hydrolyzes：120 DEG C are cooled to, 7.5 parts of phosphoric acid and 100 parts of water are added, hydrolyzes 1~2h；
(3) it is condensed：It is cooled to 95 DEG C, 18.4 parts of cocondensation polycondensation monomer D is added, 111.3 parts of formaldehyde are then added, 100~
105 DEG C carry out 3~4h of condensation reaction；
(4) it neutralizes：Aforementioned condensation material, which is transferred to, to be neutralized kettle and 146 part of 32% liquid caustic soda and 265 parts of water is added, and reactant is neutralized
It is 8~10 to get to modified naphthalene series water-reducing agent to pH value.
Embodiment 5：
(1) preparation of cocondensation polycondensation monomer：
167.3 parts of itaconic acids, 53.6 parts of styrene, 58.6 parts of sodium hypophosphites and 248.9 parts of water, side are put into a kettle
Stirring side is heated to 60~70 DEG C；It is 5~7 that 75.8 part of 32% liquid caustic soda, which is added, and adjusts the pH value of reaction system；By 190.0 parts of propylene
Sour hydroxyl ethyl ester and 5.8 parts of potassium peroxydisulfates are added in 200 parts of water, are made into mixed liquor, and drip off in 3~4h；Rear constant temperature is added dropwise
React 2~3h；Stop heating, is cooled to 40 DEG C or so dischargings to get cocondensation polycondensation monomer E.
(2) a kind of modified naphthalene series water-reducing agent, preparation process are as follows：
(1) sulfonation：120 parts of crude naphthalenes and 55 parts of betanaphthols are put into reaction kettle and are heated and are melted to 130~135 DEG C, are added
Enter 148.7 part of 98% concentrated sulfuric acid, in 160 DEG C of 3~4h of sulfonating reaction；
(2) it hydrolyzes：120 DEG C are cooled to, 15.2 parts of phosphoric acid and 100 parts of water are added, hydrolyzes 1~2h；
(3) it is condensed：It is cooled to 95 DEG C, 33.2 parts of cocondensation polycondensation monomer E is added, 104.5 parts of formaldehyde are then added, 100~
105 DEG C carry out 3~4h of condensation reaction；
(4) it neutralizes：Aforementioned condensation material, which is transferred to, to be neutralized kettle and 149 part of 32% liquid caustic soda and 254 parts of water is added, and reactant is neutralized
It is 8~10 to get to modified naphthalene series water-reducing agent to pH value.
Comparative example：
A kind of synthesis of common naphthalene water reducer includes the following steps：
(1) sulfonation：162 parts of industrial naphtho- heating are put into reaction kettle and are melted to 130~135 DEG C, and 170 part 98% of addition is dense
Sulfuric acid, in 160 DEG C of 3~4h of sulfonating reaction；
(2) it hydrolyzes：120 DEG C are cooled to, 100 parts of water are added, hydrolyzes 1~2h；
(3) it is condensed：95 DEG C are cooled to, 110 parts of formalins are added, 3~4h of condensation reaction is carried out at 100 DEG C；
(4) it neutralizes：Aforementioned condensation material, which is transferred to, to be neutralized kettle and 140 part of 32% liquid caustic soda and 243 parts of water is added, and reactant is neutralized
It is 8~10 to get to product to pH value.
Application Example 1：
In order to evaluate the performance of modified naphthalene series water-reducing agent of the invention, according to GB/T8077-2012《Concrete admixture is even
Matter test method》Different flowing degree of net paste of cement experiments are carried out.Three kinds of cement are reference cement, China Water respectively in experiment
42.5 cement of conch PO of mud Co., Ltd., Factory production and 42.5 cement of crane woods PO of Jiangsu He Lin Cement Co., Ltds production；
Water-reducing agent also selects the FDN naphthalene water reducers of Shandong factory to be compared, volume is other than above-described embodiment and comparative example
0.75% (being counted on the basis of the weight for rolling over solid rear cement), test result is shown in Table 1.
The flowing degree of net paste of cement of the different naphthalene water reducers of table 1
By 1 result of table as it can be seen that flowing degree of net paste of cement of the modified naphthalene series water-reducing agent in three kinds of cement of the present invention especially
It is the common naphthalene water reducer that gradual loss is totally better than in two kinds of comparative examples.
Application Example 2：
According to GB 8076-2008《Concrete admixture》Modification of the present invention is mixed in the relevant regulations of middle high efficiency water reducing agent, evaluation
Water-reducing rate, air content, setting time and the compression strength of the concrete of naphthalene water reducer.Experiment uses reference cement, fineness mould
Number is 2.6 middle sand, and the rubble of 5~20mm continuous gradings, concrete mix is cement:Sand:Stone=330:768:1152, it adjusts
Whole water consumption makes fresh concrete initial slump be 80mm ± 10mm, and the volume of water-reducing agent is 0.75% (folding of cement weight
Gu).Test result is shown in Table 2.
Table 2 mixes the concrete performance of the present invention
By 2 result of table as it can be seen that when the modified naphthalene series water-reducing agent volume of the present invention is 0.75% water-reducing rate up to 23% or more,
Slightly above common naphthalene water reducer；Air content is compared with blank group only to have a small increase, and is non-air-entraining water-reducing agent；Setting time
A degree of extension has been compared with common naphthalene water reducer, but has been had no adverse effects for 7d, 28d compression strength.
Application Example 3：
According to GB 8076-2008《Concrete admixture》The relevant regulations of middle pumping admixture, evaluation modified naphthalene series of the present invention
Water-reducing agent is re-dubbed pumping admixture and mixes air content, setting time, the slump and 1h ongoing change amount after concrete and resistance to compression
Intensity.Experiment uses reference cement, the middle sand that fineness modulus is 2.6, the rubble of 5~20mm continuous gradings, concrete mix
For cement:Sand:Stone:Water=360:864:1056:185；Pumping admixture volume is 1.2%, is formulated as naphthalene water reducer:Rosin is drawn
Gas agent:Sodium gluconate:Water=0.4:0.03:0.03:0.54, test result see the table below 3.
Table 3 mixes the concrete performance after the pumping admixture that the present invention is re-dubbed
Concrete is mixed as it can be seen that being re-dubbed after pumping admixture with the modified naphthalene series water-reducing agent of the present invention by 3 result of table, and common
Concrete is compared, and air content and 7d, 28d compression strength are substantially unaffected, and concrete slump and the degree of expansion that collapses, especially 1h
Ongoing change amount is obviously reduced, and is more advantageous to concrete long-distance transportation and pumping construction.
Although the present invention is described by embodiment, embodiment is not used for limiting the present invention.Art technology
Personnel can make various modifications and improvement, such as the adjustment of component ratio or time range in the range of the spirit of the present invention,
Effect after this adjustment is predictable, so it is equally within protection scope of the present invention.Therefore the protection of the present invention
Range should be subject to the protection domain that the identical or equivalent technical characteristic of claims hereof is defined.
Claims (5)
1. a kind of preparation method of modified naphthalene series water-reducing agent, which is characterized in that include the following steps：
Step 1: the preparation of cocondensation polycondensation monomer：
A certain amount of water, unsaturated dicarboxylic acid, styrene and sodium hypophosphite are put into a kettle, are heated under constant stirring
To 60 ~ 70 DEG C；It is 5 ~ 7 that 32% liquid caustic soda, which is added, and adjusts the pH value of reaction system；Acrylic acid hydroxy alkyl ester is added dropwise, initiator adds water to match
At mixed solution, control rate of addition drips off in 2 ~ 4h, and continues 2 ~ 4h of heat preservation at 60 ~ 70 DEG C；Stop heating, is cooled to
40 DEG C or so dischargings are to get cocondensation polycondensation monomer；
In step 1, the styrene:Unsaturated dicarboxylic acid:The molar ratio of acrylic acid hydroxy alkyl ester is (0.25 ~ 0.5):1:
(1.0 ~ 1.6), sodium hypophosphite dosage are the 12 ~ 20% of monomer gross mass, and initiator amount is the 0.5 ~ 2% of monomer gross mass；
Step 2: the preparation of modified naphthalene series water-reducing agent：
（1）Sulfonation：The homologue of naphthalene is put into reaction kettle and heating is melted to 130 ~ 135 DEG C, and 98% concentrated sulfuric acid is added, 150 ~
170 DEG C of 3 ~ 4h of sulfonating reaction, obtain sulfonation material；The homologue of naphthalene is methyl naphthalene；
（2）Hydrolysis：100 ~ 130 DEG C are cooled to, a certain amount of phosphoric acid and water is added, hydrolyzes 1 ~ 2h；
（3）Condensation：Material through hydrolysing step is cooled to 90 ~ 105 DEG C, and cocondensation polycondensation monomer is added, adds formaldehyde, 100 ~
105 DEG C carry out 3 ~ 4h of condensation reaction；
（4）It neutralizes：Aforementioned condensation material, which is transferred to, to be neutralized kettle and 32% liquid caustic soda and water is added, and it is 8 ~ 10 that reactant, which is neutralized to pH value, i.e.,
Obtain the modified naphthalene series water-reducing agent；
In step 2, the phosphoric acid dosage is the 4 ~ 12% of concentrated sulfuric acid quality.
2. the preparation method of modified naphthalene series water-reducing agent according to claim 1, it is characterised in that：In step 1, it is described not
Saturated dicarboxylic acid is one kind in maleic acid, maleic anhydride, fumaric acid, fumaric acid anhydride, itaconic acid or citraconic acid.
3. the preparation method of modified naphthalene series water-reducing agent according to claim 1, it is characterised in that：In step 1, described third
Olefin(e) acid hydroxy alkyl ester is one kind in hydroxy-ethyl acrylate or hydroxypropyl acrylate.
4. the preparation method of modified naphthalene series water-reducing agent according to claim 1, it is characterised in that：It is described to draw in step 1
It is one or more of persulfuric acid salt, including potassium peroxydisulfate, ammonium persulfate or sodium peroxydisulfate to send out agent.
5. the preparation method of modified naphthalene series water-reducing agent according to claim 1, it is characterised in that：It is described dense in step 2
Sulfuric acid:The molar ratio of the homologue of naphthalene is (1.1 ~ 1.8):1；
The cocondensation polycondensation monomer dosage is the 5 ~ 10% of the homologue gross mass of naphthalene；
The formaldehyde:The molar ratio of the homologue of naphthalene is (0.8 ~ 1.4):1.
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| CN107043442B (en) * | 2017-02-24 | 2019-05-17 | 唐山市龙亿科技开发有限公司 | High-thin arch dam, high water reduction, the preparation method of anti-stick soil type modified naphthalene series water-reducing agent |
| CN106928420A (en) * | 2017-03-21 | 2017-07-07 | 沈丽亚 | A kind of BB acid waste liquids modified aliphatic high efficiency water reducing agent |
| CN108623745B (en) * | 2018-06-08 | 2020-03-06 | 科之杰新材料集团有限公司 | Phosphorus-containing polycarboxylate superplasticizer and preparation method thereof |
| CN115246716B (en) * | 2021-04-28 | 2023-06-09 | 山东理工大学 | Method for preparing high-performance naphthalene water reducer by using thermosetting resin composite material waste |
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| CN104592445A (en) * | 2015-01-28 | 2015-05-06 | 水利部交通运输部国家能源局南京水利科学研究院 | Organic phosphonate concrete plastic retaining agent and preparation method thereof |
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