CN102101758B - Polyether carboxylic acid water reducer and preparation method thereof - Google Patents

Polyether carboxylic acid water reducer and preparation method thereof Download PDF

Info

Publication number
CN102101758B
CN102101758B CN 201010599359 CN201010599359A CN102101758B CN 102101758 B CN102101758 B CN 102101758B CN 201010599359 CN201010599359 CN 201010599359 CN 201010599359 A CN201010599359 A CN 201010599359A CN 102101758 B CN102101758 B CN 102101758B
Authority
CN
China
Prior art keywords
initiator
water
reducing agent
maleic anhydride
alcohol ether
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN 201010599359
Other languages
Chinese (zh)
Other versions
CN102101758A (en
Inventor
马清浩
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to CN 201010599359 priority Critical patent/CN102101758B/en
Publication of CN102101758A publication Critical patent/CN102101758A/en
Application granted granted Critical
Publication of CN102101758B publication Critical patent/CN102101758B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C04B24/165—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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 carboxylic acid water reducer and preparation method thereof
Technical field
The present invention relates to a kind of the reinforcement of concrete 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 again dispersion agent or fluidizer, 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 cement, sand, stone and water.
Common water reducer mainly contains xylogen ring phosphate-gallate series, naphthalene system, melamine series, sulfamate system and polycarboxylic acid series etc.Be the application and development period of ordinary water-reducing agent the thirties to the sixties in 20th century, the water reducer of early application is mainly the organic compound such as sodium abietate, sodium lignosulfonate, stearate, it mainly is be used to improving concrete application property, solving 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 of modern construction.
Since at first developing naphthalene sulfonic acidformaldehyde condensation product high efficiency water reducing agent and West Germany's exploitation melamine superplasticizer in 1964 from Japan in 1962, 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 that water-reducing rate is high, the cement dispersion effect is good, its Main Function is decrease unit consumption of water or unit cement consumption, be used for preparing high-strength, superelevation is strong, high durability concrete, but its fatal shortcoming is that slump-loss is large, 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, therefore its high performance potentiality are large, is considered to the regeneration product of high efficiency water reducing agent.
External polycarboxylic acid series high efficiency water reducing agent is widely used in the concrete preparation, and product type is main with maleic anhydride mainly.Take Japan as example, 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 again in reaction vessel, rising temperature decompression dehydration.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 except 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 was divided into for two steps to 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, desolventizing obtained the research work of air entrained type high efficiency water reducing agent after question response was finished substantially.The water reducer that the method obtains is only soluble in alkali lye and is insoluble in water, brings very large 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 provides 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, little loss of slump, water-reducing rate are high, and preparation technology is simple, and be with low cost.
Acrylic resin water reducing agent 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 the aqueous solution that acrylamide and 2-Hydroxy ethyl acrylate form and the aqueous solution of initiator in the mixture that obtains in the step 1, maintain the temperature at 80～100 ℃ in the dropping process, time for adding is 2～5 hours;
Step 3: after dropwising, 80～100 ℃ lower 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 the 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 concentration of initiator be the 2-5 % by weight.Preferably, time for adding 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 obtains in the step 1 and be 3% Potassium Persulphate initiator, maintain the temperature at 90 ℃ in the dropping process, time for adding is 3-3.5 hour;
Step 3: after dropwising, 80～100 ℃ of lower isothermal reactions approximately 5 hours;
Step 4: filter.
Productive rate is 94%.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 the 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%.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%.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%.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%.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%.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%.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 Ratio after adding to respectively water reducer of the present invention and the described water reducer of Comparative Examples in the Lafarge cement
Figure BSA00000393808100051
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
"-" represents reaction process and is 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, then pull up bucket, 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 (7)

1. polyether-type acrylic resin water reducing agent, it is prepared from by polypropylene alcohol ether, MALEIC ANHYDRIDE, methylpropene sodium sulfonate, acrylamide, 2-Hydroxy ethyl acrylate, initiator and water, and 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.
2. polyether-type acrylic resin water reducing agent according to claim 1, 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.
3. each described polyether-type acrylic resin water reducing agent according to claim 1-2, wherein said polypropylene alcohol ether is CH 2=CHCH 2O (CH 2CH 2O) nH, wherein n=10-60.
4. each described polyether-type acrylic resin water reducing agent according to claim 1-2, wherein said initiator is ammonium persulphate, Potassium Persulphate or Sodium Persulfate.
5. the preparation method of each described polyether-type acrylic resin water reducing agent according to claim 1-4, it comprises:
Step 1: polypropylene 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 the aqueous solution that acrylamide and 2-Hydroxy ethyl acrylate form and the aqueous solution of initiator in the mixture that obtains in the step 1, maintain the temperature at 80～100 ℃ in the dropping process, time for adding is 2～5 hours;
Step 3: after dropwising, 80～100 ℃ lower isothermal reaction 2-8 hour;
Step 4: filter.
6. method according to claim 5, wherein in the step 2 in the initiator solution concentration of initiator be the 2-5 % by weight.
7. each described method according to claim 5-6, wherein time for adding described in the step 2 is 3-4 hour, constant temperature time described in the step 3 is 4-5 hour.
CN 201010599359 2010-12-22 2010-12-22 Polyether carboxylic acid water reducer and preparation method thereof Expired - Fee Related CN102101758B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 201010599359 CN102101758B (en) 2010-12-22 2010-12-22 Polyether carboxylic acid water reducer and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 201010599359 CN102101758B (en) 2010-12-22 2010-12-22 Polyether carboxylic acid water reducer and preparation method thereof

Publications (2)

Publication Number Publication Date
CN102101758A CN102101758A (en) 2011-06-22
CN102101758B true CN102101758B (en) 2013-01-02

Family

ID=44154848

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 201010599359 Expired - Fee Related CN102101758B (en) 2010-12-22 2010-12-22 Polyether carboxylic acid water reducer and preparation method thereof

Country Status (1)

Country Link
CN (1) CN102101758B (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103359971B (en) * 2013-07-22 2015-03-04 中核混凝土股份有限公司 Nuclear-power concrete air-entraining polycarboxylic acid additive
CN103723944B (en) * 2014-01-02 2015-04-22 山东省泰和水处理有限公司 Efficient concrete water reducer and preparation method thereof
CN104386945A (en) * 2014-10-31 2015-03-04 安徽省阜南绿原化工有限公司 Anti-freezing water reducer capable of improving flowability of concrete and preparation method of anti-freezing water reducer
CN104402298A (en) * 2014-10-31 2015-03-11 安徽省阜南绿原化工有限公司 Synergist-added water-reducing agent causing no corrosion to reinforcement steel bar, and preparation method thereof
CN104761688A (en) * 2015-03-23 2015-07-08 东北大学 An early-strength type polycarboxylic acid water reducer and a preparing method thereof
CN105924030B (en) * 2016-04-29 2018-07-20 华侨大学 Esters polycarboxylic acid concrete additive of chitosan-containing and preparation method thereof
CN109336491A (en) * 2018-09-10 2019-02-15 张程玙 Hydraulic engineering frost-resistant concrete and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1620371A1 (en) * 2003-04-08 2006-02-01 Nippon Shokubai Co., Ltd. Cement admixture and cement composition
CN101205127A (en) * 2007-11-21 2008-06-25 厦门市建筑科学研究院集团股份有限公司 Formula of sustained release type polycarboxylic acid series high-performance dehydragent and method for manufacturing same
CN101338011A (en) * 2008-08-13 2009-01-07 大连市铭源全科技开发有限公司 Process for synthesizing high performance water reducing agent of polyocarboxy acid
CN101386489A (en) * 2008-09-12 2009-03-18 苏州弗克新型建材有限公司 Polycarboxylate dehydragent and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6869998B2 (en) * 2003-06-23 2005-03-22 Geo Specialty Chemicals, Inc. Concrete or cement dispersant and method of use

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1620371A1 (en) * 2003-04-08 2006-02-01 Nippon Shokubai Co., Ltd. Cement admixture and cement composition
CN101205127A (en) * 2007-11-21 2008-06-25 厦门市建筑科学研究院集团股份有限公司 Formula of sustained release type polycarboxylic acid series high-performance dehydragent and method for manufacturing same
CN101338011A (en) * 2008-08-13 2009-01-07 大连市铭源全科技开发有限公司 Process for synthesizing high performance water reducing agent of polyocarboxy acid
CN101386489A (en) * 2008-09-12 2009-03-18 苏州弗克新型建材有限公司 Polycarboxylate dehydragent and preparation method thereof

Also Published As

Publication number Publication date
CN102101758A (en) 2011-06-22

Similar Documents

Publication Publication Date Title
CN102101758B (en) Polyether carboxylic acid water reducer and preparation method thereof
CN101497507B (en) High-early strength antifreezing polycarboxylate high performance water reducing agent and preparation
CN102391435B (en) Slump-retaining polycarboxylic acid type water reducing agent and preparation method thereof
CN102161572B (en) Polyester type carboxylic acid series water reducing agent and preparation method thereof
CN102718427B (en) Sulfonyl modified carboxylic acid water-reducing agent and preparation method thereof
CN108192039B (en) Rapid hardening super early strength polycarboxylate superplasticizer and preparation method thereof
CN102718426A (en) Modified carboxylic acid water-reducing agent and preparation method thereof
CN109337024B (en) Preparation method of retarding polycarboxylate superplasticizer
CN107686540B (en) Preparation method of early-strength polycarboxylate superplasticizer
CN102211913B (en) Cement-based grouting material containing polyester type carboxylic acid water reducing agent and preparation method thereof
CN102731730A (en) Hydrogen peroxide auxiliarily-initiated carboxylic acid water reducer and its preparation method
CN108218284B (en) Concrete water reducing agent composition
CN102951866A (en) Ascorbic acid modified carboxylic water reducer and preparation method thereof
CN100465123C (en) Method of preparing poly carboxylic acid series water reducer using maleic anhydride
CN102173638A (en) Polycarboxylate water reducer and preparation method thereof
CN102731015A (en) Polyester-base carboxylic acid water reducer and its preparation method
CN102276180B (en) Modified melamine water reducer and preparation method thereof
CN102372829A (en) Preparation method of concrete water reducer
CN109912752A (en) A kind of water-reducing agent and preparation method thereof
CN109306021B (en) Starch sulfate retarding superplasticizer and preparation method thereof
CN112608423A (en) Preparation method of viscosity-reducing and mud-resisting polycarboxylate superplasticizer
CN115926066A (en) Polycarboxylate superplasticizer and preparation method thereof
CN109912750A (en) A kind of water-reducing agent and preparation method thereof
CN102731009A (en) Sulfo group-containing polyester carboxylic acid water reducer and its preparation method
CN102211909B (en) Cement-based grouting material containing polyether carboxylic acid type water reducing agent and preparation method of cement-based grouting material

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20130102

Termination date: 20131222