CN102101758A

CN102101758A - Polyether carboxylic acid water reducer and preparation method thereof

Info

Publication number: CN102101758A
Application number: CN 201010599359
Authority: CN
Inventors: 马清浩
Original assignee: Individual
Current assignee: Individual
Priority date: 2010-12-22
Filing date: 2010-12-22
Publication date: 2011-06-22
Anticipated expiration: 2030-12-22
Also published as: CN102101758B

Abstract

The invention provides a polyether carboxylic acid water reducer and a preparation method thereof. The water reducer is prepared from the following components: polypropylene alcohol ether, maleic anhydride, sodium methylallyl sulfonate, acrylamide, 2-hydroxyethyl acrylate, initiator and water.

Description

A kind of polyether-type carboxylic acid water reducing agent and preparation method thereof

Technical field

The present invention relates to a kind of concrete with admixture and preparation method thereof, relate in particular to a kind of polycarboxylic acids dehydragent and preparation method thereof.

Background technology

Water reducer is called dispersion agent or fluidizer again, during owing to use the water consumption of fresh concrete is reduced, and therefore gains the name.In the modern concrete technical field, water reducer is one of admixture that improves rheological property of concrete, has been taken as five component of concrete except that cement, sand, stone and water.

Common water reducer mainly contains xylogen ring phosphate-gallate series, naphthalene system, trimeric cyanamide system, sulfamate system and polycarboxylic acid series etc.Be the application and the developing period of ordinary water-reducing agent the thirties to the sixties in 20 century, the early stage water reducer that uses is mainly organic compound such as sodium abietate, sodium lignosulfonate, stearate, it mainly is to be used to improve Concrete Construction, solves the endurance issues such as freeze-thaw-of concrete road surface.But along with improving constantly of construction requirement, the water-reducing effect of the water reducer that these are early stage can not satisfy the needs that modern project is built.

Since at first developing naphthalene sulfonic acidformaldehyde condensation product high efficiency water reducing agent and West Germany's exploitation trimeric cyanamide series high-efficiency water-reducing agent in 1964 from Japan in 1962, the exploitation and the application period of high efficiency water reducing agent have been entered, advantageously promoted the development of concrete technology, the outstanding feature of these two series of high efficiency water reducers is water-reducing rate height, the cement dispersion effect is good, it mainly acts on is to reduce unit consumption of water or unit cement consumption significantly, be used to prepare high-strength, superelevation is strong, high durability concrete, but its fatal shortcoming is that slump-loss is big, and formaldehyde volatilization environmental pollution is serious in the preparation process.And polycarboxylic acid series high efficiency water reducing agent blending amount is low, but to the good dispersity of concrete (cement), slump retaining is good, and easily modification, so its high performance potentiality are big, is considered to the regeneration product of high efficiency water reducing agent.

External polycarboxylic acid series high efficiency water reducing agent is extensive use of in the concrete preparation, and product type is main with maleic anhydride mainly.With Japan is example, and the product synthetic method is mainly: the first step, under the nitrogen protection condition, methyl alcohol and oxyethane react under certain temperature and pressure, add NaOH, elevated temperature decompression dehydration again in reaction vessel.Subsequently, in mixture, add a certain amount of chlorallylene, when mixture basicity is reduced to a stationary value, use the HCl neutralise mixt, separate obtaining allyl ethers.Second step: as solvent, under nitrogen protection, the allyl ethers and the maleic anhydride that obtain with the first step reaction carry out polyreaction, steam and remove toluene solvant, obtain maleic anhydride series high performance concrete water reducer with toluene.

The domestic relevant report that polycarboxylic acid series high efficiency water reducing agent is also arranged in recent years.Its use raw material generally by unsaturated carboxylic acid class (vinylformic acid, methacrylic acid, maleic anhydride), polyoxy alkene (polyoxyethylene, polyoxyethylene glycol etc.), unsaturated carboxylate type, contain the unsaturated monomer of sulfonic acid group etc.; Its synthesis step generally be divided into two the step carry out.As the polycarboxylic acid series water reducing agents for efficient aerocrote reported among the CN1316398A tosic acid do catalyzer, Resorcinol do stopper, dibenzoyl peroxide do the initiator condition little with the methacrylic acid polymerization reaction take place, obtain bleed type high efficiency water reducing agent except that desolvating question response is finished substantially after.The water reducer that this method obtains is only soluble in alkali lye and is insoluble in water, brings very big inconvenience to use.CN1800076A also discloses a kind of acrylic acid series multiple copolymer analog high efficiency water reducing agent, the shared umber of its each raw material is: 100 parts of vinylformic acid or derivatives thereofs, 150～450 parts of polyoxy alkenes, sulfonic acid are 10～80 parts in derivative, 450～800 parts of deionized water solvents, 0.5～6 part of catalyzer, 0.1～5 part of stopper, 5～30 parts of Virahol chain-transfer agents, 0.5～5 part of initiator, and the add-on of NaOH solution is to make the pH value of product reach 6～8.But the method reaction process that this patent provided is difficult to control, and water-reducing rate and slump retention value still are not very desirable yet.

Summary of the invention

The present invention provides a kind of novel water reducer in order to overcome above-mentioned deficiency of the prior art, and this water reducer environmental protection, slump-loss is little, water-reducing rate is high, and preparation technology is simple, and is with low cost.

Acrylic acid series water reducer of the present invention is prepared from by following component: polypropylene alcohol ether, MALEIC ANHYDRIDE, methylpropene sodium sulfonate, acrylamide, 2-Hydroxy ethyl acrylate, initiator and water.Preferably, the parts by weight of each component are: 100 parts in polypropylene alcohol ether 25-40 part, MALEIC ANHYDRIDE 3-6 part, methylpropene sodium sulfonate 1-6 part, acrylamide 0.5-4 part, 2-Hydroxy ethyl acrylate 1-5 part, initiator 0.5-4 part and water.

Further preferably, the parts by weight of each component are: 100 parts in polypropylene alcohol ether 30-35 part, MALEIC ANHYDRIDE 3.5-4 part, methylpropene sodium sulfonate 2-3 part, acrylamide 1-2 part, 2-Hydroxy ethyl acrylate 2-3 part, initiator 1-2 part and water.

Preferred described polypropylene alcohol ether is CH ₂=CHCH ₂O (CH ₂CH ₂O) _nH, wherein n=10-60.Preferred described initiator is ammonium persulphate, Potassium Persulphate or Sodium Persulfate.

The preparation method of described water reducer comprises:

Step 1: propylene alcohol ether, MALEIC ANHYDRIDE and methylpropene sodium sulfonate are mixed with the aqueous solution, join in the reactor, stir, be warming up to 80～100 ℃;

Step 2: drip acrylamide and the aqueous solution of 2-Hydroxy ethyl acrylate formation and the aqueous solution of initiator in the mixture that obtains in step 1, maintain the temperature at 80～100 ℃ in the dropping process, the dropping time is 2～5 hours;

Step 3: after dropwising, 80～100 ℃ following isothermal reaction 2-8 hour;

Step 4: filter.

Preferably, in the described aqueous solution of step 1, with respect to the water of 100 weight parts, the parts by weight of propylene alcohol ether, MALEIC ANHYDRIDE and methylpropene sodium sulfonate are respectively: 100-150 weight part, 15-25 weight part, 1-15 weight part.

Preferably, in the aqueous solution that described acrylamide of step 2 and 2-Hydroxy ethyl acrylate form, with respect to the water of 100 weight parts, the parts by weight of acrylamide and 2-Hydroxy ethyl acrylate are respectively 12-18 weight part and 15-25 weight part.In the step 2 in the initiator solution initiator concentration be 2-5 weight %.Preferably, the time of dropping described in the step 2 is 3-4 hour, and constant temperature time described in the step 3 is 4-5 hour

Embodiment

Embodiment 1

Step 1: with 320Kg propylene alcohol ether CH ₂=CHCH ₂O (CH ₂CH ₂O) _nH (wherein n=10-60), 420Kg MALEIC ANHYDRIDE and 50Kg methylpropene sodium sulfonate join in the 300Kg water and are mixed with the aqueous solution, join in the reactor, stir, and are warming up to 90 ℃;

Step 2: the aqueous solution that drips the aqueous solution of 13Kg acrylamide and 26Kg 2-Hydroxy ethyl acrylate and the formation of 140Kg water and 860Kg concentration in the mixture that in step 1, obtains and be 3% Potassium Persulphate initiator, maintain the temperature at 90 ℃ in the dropping process, the dropping time is 3-3.5 hour;

Step 3: after dropwising, about 5 hours of 80～100 ℃ of following isothermal reactions;

Step 4: filter.

Productive rate is 94%.The slump retention value and the water-reducing rate value of products obtained therefrom see Table 1.

Embodiment 2

Other step is identical with embodiment 1, and difference is that replacing the n value with 320Kg propylene alcohol ether is the CH of 200-300 ₂=CHCH ₂O (CH ₂CH ₂O) _nH replaces the CH of n=10-60 among the embodiment 1 ₂=CHCH ₂O (CH ₂CH ₂O) _nH.Productive rate is 90%.The slump retention value and the water-reducing rate value of products obtained therefrom see Table 1.

Embodiment 3

Other step is identical with embodiment 1, and difference is the consumption of acrylamide is reduced to 8Kg.Productive rate is 80%.The slump retention value and the water-reducing rate value of products obtained therefrom see Table 1.

Embodiment 4

Other step is identical with embodiment 1, and difference is in the step 2 temperature to be remained on 80 ℃, rather than 90 ℃.Productive rate is 93%.The slump retention value and the water-reducing rate value of products obtained therefrom see Table 1.

Comparative Examples 1

Other step is identical with embodiment 1, and difference is to replace 420Kg MALEIC ANHYDRIDE described in the step 1 with the 420Kg terephthalic anhydride.Productive rate is 95%.The slump retention value and the water-reducing rate value of products obtained therefrom see Table 1.

Comparative Examples 2

Other step is identical with embodiment 1, and difference is not add MALEIC ANHYDRIDE.Productive rate is 95%.The slump retention value and the water-reducing rate value of products obtained therefrom see Table 1.

Comparative Examples 3

Other step is identical with embodiment 1, and difference is not add acrylamide.Productive rate is 90%.The slump retention value and the water-reducing rate value of products obtained therefrom see Table 1.

Comparative Examples 4

Other step is identical with embodiment 1, and difference is to replace 2-Hydroxy ethyl acrylate with Virahol.

Table 1:

Performance after adding to water reducer of the present invention and the described water reducer of Comparative Examples in the Lafarge cement respectively relatively

Embodiment 4	0.6％	27.5	168	*
					Comparative Examples 1	0.6％	23.9	110	*
Comparative Examples 2	0.6％	15.8	120	*

Comparative Examples 3	0.6％	25.8	140	*
					Comparative Examples 4	-	-	-	-

Illustrate: " * " representative reaction is carried out smoothly

On behalf of reaction process, "-" be difficult to control

The testing method of the slump wherein: with a 100mm suitable for reading, end opening 200mm, the trumpet-shaped slump bucket of high 300mm, tamping behind the penetration concrete, pull up bucket then, concrete produces the slump phenomenon because of deadweight, deduct the height of concrete vertex after the slump with bucket high (300mm), be called slump, unit is mm; Water-reducing rate is according to the method test of stipulating among the GB8076-2008.

Claims

1. polyether-type acrylic acid series water reducer, it is prepared from by polypropylene alcohol ether, MALEIC ANHYDRIDE, methylpropene sodium sulfonate, acrylamide, 2-Hydroxy ethyl acrylate, initiator and water.

2. the described polyether-type acrylic acid series of claim 1 water reducer, wherein the parts by weight of each component are: 100 parts in polypropylene alcohol ether 25-40 part, MALEIC ANHYDRIDE 3-6 part, methylpropene sodium sulfonate 1-6 part, acrylamide 0.5-4 part, 2-Hydroxy ethyl acrylate 1-5 part, initiator 0.5-4 part and water.

3. the described polyether-type acrylic acid series of claim 2 water reducer, wherein the parts by weight of each component are: 100 parts in polypropylene alcohol ether 30-35 part, MALEIC ANHYDRIDE 3.5-4 part, methylpropene sodium sulfonate 2-3 part, acrylamide 1-2 part, 2-Hydroxy ethyl acrylate 2-3 part, initiator 1-2 part and water.

4. each described polyether-type acrylic acid series water reducer of claim 1-3, wherein said polypropylene alcohol ether is CH ₂=CHCH ₂O (CH ₂CH ₂O) _nH, wherein n=10-60.

5. each described polyether-type acrylic acid series water reducer of claim 1～4, wherein said initiator is ammonium persulphate, Potassium Persulphate or Sodium Persulfate.

6. the preparation method of each described polyether-type acrylic acid series water reducer of claim 1-6, it comprises:

Step 3: after dropwising, 80～100 ℃ following isothermal reaction 2-8 hour;

Step 4: filter.

7. the described method of claim 6, wherein in the described aqueous solution of step 1, with respect to the water of 100 weight parts, the parts by weight of propylene alcohol ether, MALEIC ANHYDRIDE and methylpropene sodium sulfonate are respectively: 100-150 weight part, 15-25 weight part, 1-15 weight part.。

8. each described method of claim 6-7, wherein the preparation process of B material is: in the aqueous solution that described acrylamide of step 2 and 2-Hydroxy ethyl acrylate form, with respect to the water of 100 weight parts, the parts by weight of acrylamide and 2-Hydroxy ethyl acrylate are respectively 12-18 weight part and 15-25 weight part.

9. each described method of claim 6-8, wherein in the step 2 in the initiator solution initiator concentration be 2-5 weight %.

10. each described method of claim 6-9, wherein the time of dropping described in the step 2 is 3-4 hour, constant temperature time described in the step 3 is 4-5 hour.