CN106496433A - A kind of preparation method of polycarboxylic acid super-plasticizer - Google Patents
A kind of preparation method of polycarboxylic acid super-plasticizer Download PDFInfo
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- CN106496433A CN106496433A CN201610886605.4A CN201610886605A CN106496433A CN 106496433 A CN106496433 A CN 106496433A CN 201610886605 A CN201610886605 A CN 201610886605A CN 106496433 A CN106496433 A CN 106496433A
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- plasticizer
- polycarboxylic acid
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- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/002—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers modified by after-treatment
-
- 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
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
-
- 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
- C04B2103/32—Superplasticisers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a kind of preparation method of polycarboxylic acid super-plasticizer, belongs to polycarboxylic acid super-plasticizer preparing technical field.Polyether-ether-ketone is reacted by the present invention with oil bath heatings such as sodium borohydrides, sucking filtration obtains filtering residue 1, add soak with hydrochloric acid, sucking filtration to obtain filtering residue 2 after washing, after drying, obtain hydroxylating polyether-ether-ketone, ultrasonic disperse in dimethylformamide is added to obtain dispersion liquid, react with maleic anhydride, concentrated solution is obtained through vacuum distillation, after mixing with deionized water, allyl sulphonic acid sodium water solution and the acrylic acid stirring reactions such as addition, then reactant pH is adjusted for prepared polycarboxylic acid super-plasticizer after neutrality.Preparation process of the present invention is simple, and gained polycarboxylic acid super-plasticizer workability is good, strong with concrete adhesion, efficiently solves slump-loss soon, using the low problem of rear early strength, with good dispersion effect and protects plasticity.
Description
Technical field
The present invention relates to a kind of preparation method of polycarboxylic acid super-plasticizer, belongs to polycarboxylic acid super-plasticizer technology of preparing neck
Domain.
Background technology
With the continuous development of building industry, performance requirement more and more higher of the people to construction material, such as higher construction
Performance and intensity and durability etc..Additive is to improve the highly important component of concrete performance, can be in minimum volume feelings
The performance of concrete is greatly improved under condition.Super plasticizer is called concrete admixture, and general super plasticizer is referred to mixed
Under solidifying soil workability and cement consumption permanence condition, mixing water amount can be reduced, improve concrete strength, or in workability and strong
Under degree permanence condition, the additive of cement consumption is saved.Super plasticizer can reduce moisture needed for hardening of cement for concrete,
There is very strong peptizaiton to cement, make the physical arrangement of concrete after solidification more uniform, near and improve the strong of concrete
Degree.
Traditional naphthalenesulfonate formaldehyde condensation compound（SNF）, condensate of melamine sulfonate and formaldehyde（SMF）Deng efficiently super modeling
Agent is changed greatly due to the slump, and production technology pollutes environment, can not fully meet concrete construction and sustainable development
Requirement.Therefore, for environmental protection, the needs of economic and engineering, concrete admixture is towards high-performance, multifunction, green
The direction of change is developed, and the more excellent polycarboxylic acid super-plasticizer of research promotion performance becomes focus.The super modeling of polycarboxylic acid series high-performance
Agent is generated in the presence of initiator by the unsaturated monomer containing sulfonic acid group, hydroxy-acid group, polyoxy alkylalkenyl group etc.
The general designation of one class combed high molecular polymer, is indispensable component in high performance concrete.But its workability is poor, with coagulation
Native adhesion is weak, and slump-loss is fast, low using rear early strength.
Content of the invention
The technical problem to be solved：Poor for current polycarboxylic acid super-plasticizer workability, combined with concrete
Power is weak, and slump-loss is fast, using rear early strength low the drawbacks of, there is provided a kind of by polyether-ether-ketone and oil baths such as sodium borohydrides
Reacting by heating, sucking filtration obtain filtering residue 1, add soak with hydrochloric acid, sucking filtration to obtain filtering residue 2, obtain hydroxylating polyether-ether-ketone after drying after washing, plus
Enter ultrasonic disperse in dimethylformamide and obtain dispersion liquid, react with maleic anhydride, concentrated solution is obtained through vacuum distillation, with deionized water
After mixing, allyl sulphonic acid sodium water solution and the acrylic acid stirring reaction such as addition, then it is poly- for being obtained after neutrality to adjust reactant pH
The method of carboxylic acid super plasticizer.Preparation process of the present invention is simple, and gained polycarboxylic acid super-plasticizer workability is good, is combined with concrete
Power is strong, efficiently solves slump-loss soon, using the low problem of rear early strength, with good dispersion effect and protects plasticity.
For solving above-mentioned technical problem, the present invention using technical scheme as described below is：
（1）Weigh 15～20g polyether-ether-ketones, 10～15g sodium borohydrides and 60～80g dimethyl sulfoxide respectively and be added to three mouthfuls of burnings
In bottle, subsequently there-necked flask is put in oil bath pan, 120～125 DEG C are warming up to, after insulated and stirred reacts 4～6h, sucking filtration must be filtered
Slag 1；
（2）By the absolute ethanol washing 2～4 times of above-mentioned filtering residue 1, subsequently in mass ratio 1:10, by washing after filtering residue 1 add matter
In amount 10% hydrochloric acid of fraction, 20～30min is soaked, sucking filtration obtains filtering residue 2, puts it in baking oven, dried under the conditions of 80～90 DEG C
8～10h, obtain hydroxylating polyether-ether-ketone；
（3）By above-mentioned hydroxylating polyether-ether-ketone in mass ratio 1:5 add in dimethylformamide, surpass under 250～300W power
Sound disperses 5～10min, obtains dispersion liquid, is loaded in four-hole boiling flask, and is separately added into 30～40g maleic anhydrides and 1～3g pair
After toluenesulfonic acid, four-hole boiling flask is placed in oil bath pan, under nitrogen atmosphere protection, is warming up to 105～110 DEG C, insulated and stirred
3～4h of reaction, after reaction terminates, is cooled to room temperature, and vacuum distillation obtains concentrated solution to original volume 40%；
（4）By above-mentioned concentrated solution by volume 1:4 mix 5～10min with deionized water stirring, collect mixed liquor, and load four
In mouth flask, nitrogen is passed through in four-hole boiling flask and excludes air, and add 10% allyl sulphonic acid of mixed liquor equal-volume mass fraction
After sodium water solution, four-hole boiling flask is put in water-bath, is warming up to 80～85 DEG C, then it is separately added into 150 in four-hole boiling flask～
5% ammonium persulfate solution of 200mL acrylic acid and 3～5mL mass fractions, insulated and stirred react 3～4h；
（5）After above-mentioned reaction terminates, room temperature is cooled to, discharge to obtain reactant, by reactant 5% sodium hydroxide of mass fraction
Solution adjusts pH value to 7.0, and polycarboxylic acid super-plasticizer is obtained after regulation.
The application process of the present invention：Add polycarboxylic acid super-plasticizer obtained in the present invention in concrete, addition is mixed
The 0.28～0.32% of solidifying soil, high-speed stirred mix homogeneously.Polycarboxylic acid super-plasticizer of the present invention is effectively reduced concrete
Water consumption, reduces cement consumption, improves the mobility of concrete mix, reduces Chloride Diffusion Coefficient in Concrete, improves
The durability of concrete, after 2～3 days, up to 33.5～35.8MPa, rupture strength is up to 6.5～7.6MPa, tool for concrete crushing strength
The guarantor's plasticity having had.
Compared with additive method, Advantageous Effects are the present invention：
（1）Preparation process of the present invention is simple, and gained polycarboxylic acid super-plasticizer is good with the concrete compatibility, and imitates with good dispersion
Fruit and slump retaining；
（2）Polycarboxylic acid super-plasticizer safety of the present invention, environmental protection, water-reducing rate are high, with good reinforced effects, using rear morning
Phase intensity improves 7～9MPa.
Specific embodiment
Weigh 15～20g polyether-ether-ketones, 10～15g sodium borohydrides and 60～80g dimethyl sulfoxide first respectively to be added to
In there-necked flask, subsequently there-necked flask is put in oil bath pan, is warming up to 120～125 DEG C, after insulated and stirred reacts 4～6h, taken out
Filter to obtain filtering residue 1；By the absolute ethanol washing 2～4 times of above-mentioned filtering residue 1, subsequently in mass ratio 1:10, by washing after filtering residue 1 plus
Enter in 10% hydrochloric acid of mass fraction, soak 20～30min, sucking filtration obtains filtering residue 2, puts it in baking oven, under the conditions of 80～90 DEG C
8～10h is dried, obtain hydroxylating polyether-ether-ketone；Again by above-mentioned hydroxylating polyether-ether-ketone in mass ratio 1:5 add dimethyl methyl
In amide, under 250～300W power, 5～10min of ultrasonic disperse, obtains dispersion liquid, is loaded in four-hole boiling flask, and adds respectively
After entering 30～40g maleic anhydrides and 1～3g p-methyl benzenesulfonic acid, four-hole boiling flask is placed in oil bath pan, under nitrogen atmosphere protection,
Be warming up to 105～110 DEG C, insulated and stirred react 3～4h, reaction terminate after, be cooled to room temperature, vacuum distillation to original volume 40%,
Obtain concentrated solution；Then by above-mentioned concentrated solution by volume 1:4 mix 5～10min with deionized water stirring, collect mixed liquor, and
Load in four-hole boiling flask, nitrogen is passed through in four-hole boiling flask and excludes air, and add 10% allyl of mixed liquor equal-volume mass fraction
After base sulfonic acid sodium water solution, four-hole boiling flask is put in water-bath, is warming up to 80～85 DEG C, then is separately added into in four-hole boiling flask
5% ammonium persulfate solution of 150～200mL acrylic acid and 3～5mL mass fractions, insulated and stirred react 3～4h；Finally treat above-mentioned anti-
After should terminating, be cooled to room temperature, discharge to obtain reactant, by reactant with 5% sodium hydroxide solution of mass fraction adjust pH value to
7.0, polycarboxylic acid super-plasticizer is obtained after regulation.
Example 1
Weigh 15g polyether-ether-ketones, 10g sodium borohydrides and 60g dimethyl sulfoxide first respectively to be added in there-necked flask, subsequently will
There-necked flask is put in oil bath pan, is warming up to 120 DEG C, and after insulated and stirred reaction 4h, sucking filtration obtains filtering residue 1；Above-mentioned filtering residue 1 is used nothing
Water-ethanol washs 2 times, and subsequently in mass ratio 1:10, by washing after filtering residue 1 add in 10% hydrochloric acid of mass fraction, soak
20min, sucking filtration obtain filtering residue 2, put it in baking oven, under the conditions of 80 DEG C dry 8h, obtain hydroxylating polyether-ether-ketone；Again will
Above-mentioned hydroxylating polyether-ether-ketone in mass ratio 1:5 add in dimethylformamide, ultrasonic disperse 5min, score under 250W power
Dispersion liquid, is loaded in four-hole boiling flask, and after being separately added into 30g maleic anhydrides and 1g p-methyl benzenesulfonic acid, four-hole boiling flask is placed in
In oil bath pan, under nitrogen atmosphere protection, 105 DEG C are warming up to, insulated and stirred reacts 3h, after reaction terminates, is cooled to room temperature, subtracts
Pressure distillation obtains concentrated solution to original volume 40%；Then by above-mentioned concentrated solution by volume 1:4 mix 5min with deionized water stirring,
Mixed liquor is collected, and is loaded in four-hole boiling flask, nitrogen is passed through in four-hole boiling flask and excludes air, and add mixed liquor equal-volume matter
After amount 10% allyl sulphonic acid sodium water solution of fraction, four-hole boiling flask is put in water-bath, 80 DEG C are warming up to, then to four-hole boiling flask
In be separately added into 5% ammonium persulfate solution of 150mL acrylic acid and 3mL mass fractions, insulated and stirred reacts 3h；Finally treat above-mentioned anti-
After should terminating, be cooled to room temperature, discharge to obtain reactant, by reactant with 5% sodium hydroxide solution of mass fraction adjust pH value to
7.0, polycarboxylic acid super-plasticizer is obtained after regulation.
Add polycarboxylic acid super-plasticizer obtained in the present invention, addition for concrete 0.28%, high-speed stirring in concrete
Mix mix homogeneously.Polycarboxylic acid super-plasticizer of the present invention is effectively reduced the water consumption of concrete, reduces cement consumption, improves
The mobility of concrete mix, reduces Chloride Diffusion Coefficient in Concrete, improves the durability of concrete, coagulation after 2 days
Native comprcssive strength reaches 33.5MPa, and rupture strength reaches 6.5MPa, with good guarantor's plasticity.
Example 2
Weigh 18g polyether-ether-ketones, 13g sodium borohydrides and 70g dimethyl sulfoxide first respectively to be added in there-necked flask, subsequently will
There-necked flask is put in oil bath pan, is warming up to 123 DEG C, and after insulated and stirred reaction 5h, sucking filtration obtains filtering residue 1；Above-mentioned filtering residue 1 is used nothing
Water-ethanol washs 3 times, and subsequently in mass ratio 1:10, by washing after filtering residue 1 add in 10% hydrochloric acid of mass fraction, soak
25min, sucking filtration obtain filtering residue 2, put it in baking oven, under the conditions of 85 DEG C dry 9h, obtain hydroxylating polyether-ether-ketone；Again will
Above-mentioned hydroxylating polyether-ether-ketone in mass ratio 1:5 add in dimethylformamide, ultrasonic disperse 8min, score under 275W power
Dispersion liquid, is loaded in four-hole boiling flask, and after being separately added into 35g maleic anhydrides and 2g p-methyl benzenesulfonic acid, four-hole boiling flask is placed in
In oil bath pan, under nitrogen atmosphere protection, 108 DEG C are warming up to, insulated and stirred reacts 4h, after reaction terminates, is cooled to room temperature, subtracts
Pressure distillation obtains concentrated solution to original volume 40%；Then by above-mentioned concentrated solution by volume 1:4 mix 8min with deionized water stirring,
Mixed liquor is collected, and is loaded in four-hole boiling flask, nitrogen is passed through in four-hole boiling flask and excludes air, and add mixed liquor equal-volume matter
After amount 10% allyl sulphonic acid sodium water solution of fraction, four-hole boiling flask is put in water-bath, 83 DEG C are warming up to, then to four-hole boiling flask
In be separately added into 5% ammonium persulfate solution of 175mL acrylic acid and 4mL mass fractions, insulated and stirred reacts 4h；Finally treat above-mentioned anti-
After should terminating, be cooled to room temperature, discharge to obtain reactant, by reactant with 5% sodium hydroxide solution of mass fraction adjust pH value to
7.0, polycarboxylic acid super-plasticizer is obtained after regulation.
Add polycarboxylic acid super-plasticizer obtained in the present invention, addition for concrete 0.30%, high-speed stirring in concrete
Mix mix homogeneously.Polycarboxylic acid super-plasticizer of the present invention is effectively reduced the water consumption of concrete, reduces cement consumption, improves
The mobility of concrete mix, reduces Chloride Diffusion Coefficient in Concrete, improves the durability of concrete, coagulation after 3 days
Native comprcssive strength reaches 34.7MPa, and rupture strength reaches 7.1MPa, with good guarantor's plasticity.
Example 3
Weigh 20g polyether-ether-ketones, 15g sodium borohydrides and 80g dimethyl sulfoxide first respectively to be added in there-necked flask, subsequently will
There-necked flask is put in oil bath pan, is warming up to 125 DEG C, and after insulated and stirred reaction 6h, sucking filtration obtains filtering residue 1；Above-mentioned filtering residue 1 is used nothing
Water-ethanol washs 4 times, and subsequently in mass ratio 1:10, by washing after filtering residue 1 add in 10% hydrochloric acid of mass fraction, soak
30min, sucking filtration obtain filtering residue 2, put it in baking oven, under the conditions of 90 DEG C dry 10h, obtain hydroxylating polyether-ether-ketone；Again will
Above-mentioned hydroxylating polyether-ether-ketone in mass ratio 1:5 add in dimethylformamide, and under 300W power, ultrasonic disperse 10min, obtains
Dispersion liquid, is loaded in four-hole boiling flask, and after being separately added into 40g maleic anhydrides and 3g p-methyl benzenesulfonic acid, four-hole boiling flask is put
In oil bath pan, under nitrogen atmosphere protection, 110 DEG C are warming up to, insulated and stirred reacts 4h, after reaction terminates, is cooled to room temperature,
Vacuum distillation obtains concentrated solution to original volume 40%；Then by above-mentioned concentrated solution by volume 1:4 are mixed with deionized water stirring
10min, collects mixed liquor, and loads in four-hole boiling flask, is passed through nitrogen and excludes air, and add mixed liquor etc. in four-hole boiling flask
After 10% allyl sulphonic acid sodium water solution of volume mass fraction, four-hole boiling flask is put in water-bath, is warming up to 85 DEG C, then to four
5% ammonium persulfate solution of 200mL acrylic acid and 5mL mass fractions is separately added in mouth flask, and insulated and stirred reacts 4h；Finally treat
After above-mentioned reaction terminates, room temperature is cooled to, discharge to obtain reactant, reactant is adjusted pH with 5% sodium hydroxide solution of mass fraction
It is worth to 7.0, polycarboxylic acid super-plasticizer after regulation, is obtained.
Add polycarboxylic acid super-plasticizer obtained in the present invention, addition for concrete 0.32%, high-speed stirring in concrete
Mix mix homogeneously.Polycarboxylic acid super-plasticizer of the present invention is effectively reduced the water consumption of concrete, reduces cement consumption, improves
The mobility of concrete mix, reduces Chloride Diffusion Coefficient in Concrete, improves the durability of concrete, coagulation after 3 days
Native comprcssive strength reaches 35.8MPa, and rupture strength reaches 7.6MPa, with good guarantor's plasticity.
Claims (1)
1. a kind of preparation method of polycarboxylic acid super-plasticizer, it is characterised in that concrete preparation process is：
（1）Weigh 15～20g polyether-ether-ketones, 10～15g sodium borohydrides and 60～80g dimethyl sulfoxide respectively and be added to three mouthfuls of burnings
In bottle, subsequently there-necked flask is put in oil bath pan, 120～125 DEG C are warming up to, after insulated and stirred reacts 4～6h, sucking filtration must be filtered
Slag 1；
（2）By the absolute ethanol washing 2～4 times of above-mentioned filtering residue 1, subsequently in mass ratio 1:10, by washing after filtering residue 1 add matter
In amount 10% hydrochloric acid of fraction, 20～30min is soaked, sucking filtration obtains filtering residue 2, puts it in baking oven, dried under the conditions of 80～90 DEG C
8～10h, obtain hydroxylating polyether-ether-ketone；
（3）By above-mentioned hydroxylating polyether-ether-ketone in mass ratio 1:5 add in dimethylformamide, surpass under 250～300W power
Sound disperses 5～10min, obtains dispersion liquid, is loaded in four-hole boiling flask, and is separately added into 30～40g maleic anhydrides and 1～3g pair
After toluenesulfonic acid, four-hole boiling flask is placed in oil bath pan, under nitrogen atmosphere protection, is warming up to 105～110 DEG C, insulated and stirred
3～4h of reaction, after reaction terminates, is cooled to room temperature, and vacuum distillation obtains concentrated solution to original volume 40%；
（4）By above-mentioned concentrated solution by volume 1:4 mix 5～10min with deionized water stirring, collect mixed liquor, and load four
In mouth flask, nitrogen is passed through in four-hole boiling flask and excludes air, and add 10% allyl sulphonic acid of mixed liquor equal-volume mass fraction
After sodium water solution, four-hole boiling flask is put in water-bath, is warming up to 80～85 DEG C, then it is separately added into 150 in four-hole boiling flask～
5% ammonium persulfate solution of 200mL acrylic acid and 3～5mL mass fractions, insulated and stirred react 3～4h；
（5）After above-mentioned reaction terminates, room temperature is cooled to, discharge to obtain reactant, by reactant 5% sodium hydroxide of mass fraction
Solution adjusts pH value to 7.0, and polycarboxylic acid super-plasticizer is obtained after regulation.
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| CN110656492A (en) * | 2019-10-15 | 2020-01-07 | 吉林大学 | High-performance oil-water separation material based on polyether-ether-ketone, preparation method and application thereof |
| CN114304824A (en) * | 2022-01-14 | 2022-04-12 | 北京华夏理想证章有限公司 | Lasting wear-resistant souvenir badge and preparation method thereof |
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Application publication date: 20170315 |