CN102731015A - Polyester-base carboxylic acid water reducer and its preparation method - Google Patents
Polyester-base carboxylic acid water reducer and its preparation method Download PDFInfo
- Publication number
- CN102731015A CN102731015A CN2012102103060A CN201210210306A CN102731015A CN 102731015 A CN102731015 A CN 102731015A CN 2012102103060 A CN2012102103060 A CN 2012102103060A CN 201210210306 A CN201210210306 A CN 201210210306A CN 102731015 A CN102731015 A CN 102731015A
- Authority
- CN
- China
- Prior art keywords
- water
- weight part
- acid
- water reducer
- initiator
- 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.)
- Pending
Links
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention provides a polyester-base carboxylic acid water reducer and its preparation method. Raw materials for preparing the water reducer comprise: allyl alcohol polyethenoxy ether or methyl allyl alcohol polyethenoxy ether, acrylic acid, a chain transferring agent, a catalyst, antalkali and water. The water reducer has advantages of environmental protection, small slump loss and high water-reducing rate. In addition, a preparation technology of the water reducer is simple and requires low cost.
Description
Technical field
The present invention relates to a kind of concrete with admixture and preparation method thereof, relate in particular to a kind of polyester based carboxylic-acid water reducer 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 concrete technology field, water reducer is one of admixture that improves rheological property of concrete in modern times, 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 cpds such as sodium abietate, sodium lignosulfonate, stearate; It mainly is to be used to improve Concrete Construction property, 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 got into; 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, and 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 that high-strength, superelevation is strong, high durability concrete, but its fatal shortcoming is that slump-loss is big, 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 dispersivity of concrete (cement), slump retaining is good, and easy 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 widely used in the concrete preparation, and product type is main with maleic anhydride series mainly.With Japan is example, and the product compound method is mainly: the first step, under the nitrogen protection condition, methyl alcohol and oxyethane react under certain temperature and pressure, in reaction vessel, add NaOH, elevated temperature decompression dehydration again.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, methylacrylic acid, maleic anhydride), polyoxy alkene (T 46155, 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, BPO do the initiator condition little with the methylacrylic acid polymerization reaction take place, obtain bleed type high efficiency water reducing agent except that desolvating question response is accomplished basically 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 verivate, 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.
In addition; A kind of poly carboxylic acid series water reducer is also all disclosed among CN101955333A and the CN102268121A; But the former has wherein used the expensive sulphonate of price comparison, and the latter has used the acrylamide group methyl propene sulfonic acid, and temperature of reaction is than higher; Reaction process is difficult with control, needs vacuum or nitrogen protection.
Summary of the invention
The present invention provides a kind of novel water reducer and preparation method thereof 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.Especially; The present invention is surprised to find that, the water reducer with the composition adjustment of each raw material obtains within the scope of the invention need not to use comparatively expensive sulphonate in its preparation process; Need not to adopt the condition of pyroreaction; Also need not nitrogen protection or vacuumize, but compare, have and be equal to or more excellent water-reducing property with water reducer of the prior art.
The present invention at first provides a kind of polyester based carboxylic-acid water reducer, and its preparation raw material comprises: allyl alcohol polyethenoxy ether or methallyl alcohol Soxylat A 25-7, vinylformic acid, chain-transfer agent, initiator, alkaline neutraliser, water.
Preferably; Above-mentioned polyester based carboxylic-acid water reducer, it is got by the feedstock production of following weight parts: allyl alcohol polyethenoxy ether or methallyl alcohol Soxylat A 25-7 1600-2000, vinylformic acid 250-300, chain-transfer agent 6-10, initiator 16-20, alkaline neutraliser 20-100, water 3000-4000.
Preferably, the consumption of said allyl alcohol polyethenoxy ether or methallyl alcohol Soxylat A 25-7 is 1800-1850, preferably; Said acrylic acid consumption is 250-280, and preferably, the consumption of said chain-transfer agent is 8-10; Preferably; The consumption of said initiator is 17-19, and preferably, the consumption of said alkaline neutraliser is 35-40, water 3200-3500.
Preferably, above-mentioned polyester based carboxylic-acid water reducer, wherein said chain-transfer agent is a thiohydracrylic acid, and preferably, said initiator is an ammonium persulphate, and more preferably said alkaline neutraliser is a sodium hydroxide.
Preferably, above-mentioned polyester based carboxylic-acid water reducer, the preparation method of wherein said water reducer comprises:
(A) the big monomer allyl alcohol polyethenoxy ether of 1600-2000 weight part or methallyl alcohol Soxylat A 25-7 are added in the water of 2000-2500 weight part as bed material;
(B) initiator of 16-20 weight part is dissolved in the water of 600-700 weight part as material I;
(C) with in the chain-transfer agent of 6-10 weight part, the water that the 250-300 parts by weight of acrylic is dissolved in the 400-500 weight part as material II;
(D) in bed material, add pan feeding I and material II,, cool to 20-50 ℃, add the alkaline neutraliser aqueous solution 100-200 weight part of 20-50% 50-80 ℃ of reaction 1-3 hour.
Preferably, above-mentioned polyester based carboxylic-acid water reducer expects that wherein I and the mode that material II takes to drip at the uniform velocity join in the bed material, and the dropping time of the dropping time ratio material II of material I is long.
In addition, the present invention also provides a kind of preparation method of polyester based carboxylic-acid water reducer, comprising:
(A) the big monomer allyl alcohol polyethenoxy ether of 1600-2000 weight part or methallyl alcohol Soxylat A 25-7 are added in the water of 2000-2500 weight part as bed material;
(B) initiator of 16-20 weight part is dissolved in the water of 600-700 weight part as material I;
(C) with in the chain-transfer agent of 6-10 weight part, the water that the 250-300 parts by weight of acrylic is dissolved in the 400-500 weight part as material II;
(D) in bed material, add pan feeding I and material II,, cool to 20-50 ℃, add the alkaline neutraliser aqueous solution 100-200 weight part of 20-50% 50-80 ℃ of reaction 1-3 hour.Preferably, use the alkaline neutraliser aqueous solution 100-150 weight part of 25-35%.
Preferably, aforesaid method expects that wherein I and the mode that material II takes to drip at the uniform velocity drip simultaneously in bed material, the control rate of addition, and the dropping time of the dropping time ratio material II of feasible material I is long.
Preferably, aforesaid method, wherein said chain-transfer agent is a thiohydracrylic acid, and preferably, said initiator is an ammonium persulphate, and more preferably said alkaline neutraliser is a sodium hydroxide.
Preferably, aforesaid method, wherein temperature remains between 55-65 ℃ in material I and material II dropping process.
Embodiment
Embodiment 1
The big monomer methallyl alcohol Soxylat A 25-7 (molecular weight is 1800-2500) of 1800Kg is added in the water of 2100Kg as the still bed material.The ammonium persulphate of 1.5Kg is dissolved in the 680Kg water as material I.The vinylformic acid of the thiohydracrylic acid of 9Kg, 270Kg is dissolved in the water of 450Kg and expects as II.
In the still bed material, add pan feeding I and material II, expect that wherein I added with 3 and a half hours, material II added with 3 hours; Temperature in the reinforced process is controlled at 60 ℃, behind reinforced the end, and insulation reaction 1-1.5 hour; Cool to below 50 ℃, add 30% aqueous sodium hydroxide solution 120Kg.Promptly make required water reducer, productive rate is 94%.The slump retention value and the water-reducing rate value of products obtained therefrom are seen table 1.
Embodiment 2
Other step is identical with embodiment 1, and difference is to replace with the vinylformic acid of 250Kg the vinylformic acid of 270Kg among the embodiment 1.Productive rate is 92%.The slump retention value and the water-reducing rate value of products obtained therefrom are seen table 1.
Embodiment 3
Other step is identical with embodiment 1, and difference is to replace with the 10Kg Virahol thiohydracrylic acid of 10Kg among the embodiment 1.Productive rate is 90%.The slump retention value and the water-reducing rate value of products obtained therefrom are seen table 1.
Embodiment 4
Other step is identical with embodiment 1, and difference is that the consumption of methallyl alcohol Soxylat A 25-7 is 2000Kg.Productive rate is 95%.The slump retention value and the water-reducing rate value of products obtained therefrom are seen table 1.
Embodiment 5
Other step is identical with embodiment 1, and difference is to replace ammonium persulphate with Lucidol.Productive rate is 93%.The slump retention value and the water-reducing rate value of products obtained therefrom are seen table 1.
Comparative Examples 1
Other step is identical with embodiment 1, and difference is that the consumption of methallyl alcohol Soxylat A 25-7 is 1200Kg.Productive rate is 93%.The slump retention value and the water-reducing rate value of products obtained therefrom are seen table 1.
Comparative Examples 2
Other step is identical with embodiment 1, and difference is to replace with 135Kg vinylformic acid and 135Kg methylene-succinic acid the vinylformic acid of 270Kg among the embodiment 1.Productive rate is 94%.The slump retention value and the water-reducing rate value of products obtained therefrom are seen table 1.
Comparative Examples 3
Other step is identical with embodiment 1, and difference is with the methylpropene sodium sulfonate that also comprises 20Kg among the said material II.Productive rate is 92%.The slump retention value and the water-reducing rate value of products obtained therefrom are seen table 1.
Comparative Examples 4
Other step is identical with embodiment 1, difference with said acrylic acid consumption be 200Kg, rather than 270Kg.Productive rate is 70%.The slump retention value and the water-reducing rate value of products obtained therefrom are seen table 1.
Table 1:
Performance after adding to water reducer of the present invention and the said water reducer of Comparative Examples in the Lafarge cement respectively relatively
Explain: " * " 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, deducts 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 (10)
1. polyester based carboxylic-acid water reducer, its preparation raw material comprises: allyl alcohol polyethenoxy ether or methallyl alcohol Soxylat A 25-7, vinylformic acid, chain-transfer agent, initiator, alkaline neutraliser, water.
2. the described polyester based carboxylic-acid of claim 1 water reducer, it is got by the feedstock production of following weight parts: allyl alcohol polyethenoxy ether or methallyl alcohol Soxylat A 25-7 1600-2000, vinylformic acid 250-300, chain-transfer agent 6-10, initiator 16-20, alkaline neutraliser 20-100, water 3000-4000.
3. the described polyester based carboxylic-acid of claim 2 water reducer, it is got by the feedstock production of following weight parts: allyl alcohol polyethenoxy ether or methallyl alcohol Soxylat A 25-7 1800-1850, vinylformic acid 250-280, chain-transfer agent 8-10, initiator 17-19, alkaline neutraliser 35-40, water 3200-3500.
4. the described polyester based carboxylic-acid of claim 3 water reducer, wherein said chain-transfer agent is a thiohydracrylic acid, and preferably, said initiator is an ammonium persulphate, and more preferably said alkaline neutraliser is a sodium hydroxide.
5. each described polyester based carboxylic-acid water reducer of claim 1～2, the preparation method of wherein said water reducer comprises:
(A) the big monomer allyl alcohol polyethenoxy ether of 1600-2000 weight part or methallyl alcohol Soxylat A 25-7 are added in the water of 2000-2500 weight part as bed material;
(B) initiator of 16-20 weight part is dissolved in the water of 600-700 weight part as material I;
(C) with in the chain-transfer agent of 6-10 weight part, the water that the 250-300 parts by weight of acrylic is dissolved in the 400-500 weight part as material II;
(D) in bed material, add pan feeding I and material II,, cool to 20-50 ℃, add the alkaline neutraliser aqueous solution 100-200 weight part of 20-50% 50-80 ℃ of reaction 1-3 hour.
6. the described polyester based carboxylic-acid of claim 5 water reducer expects that wherein I and the mode that material II takes to drip at the uniform velocity join in the bed material, and the dropping time of the dropping time ratio material II of material I is long.
7. the preparation method of each described polyester based carboxylic-acid water reducer of claim 1～4 comprises: (A) big monomer allyl alcohol polyethenoxy ether or methallyl alcohol Soxylat A 25-7 are added in the entry as bed material; (B) initiator is dissolved in the water as material I; (C) chain-transfer agent and vinylformic acid are dissolved in the water as material II; (D) in bed material, add pan feeding I and material II,, cool to 20-50 ℃, add the alkaline neutraliser aqueous solution and neutralize 50-80 ℃ of reaction 1-3 hour.
8. the described method of claim 7, it comprises the steps:
(A) the big monomer allyl alcohol polyethenoxy ether of 1600-2000 weight part or methallyl alcohol Soxylat A 25-7 are added in the water of 2000-2500 weight part as bed material;
(B) initiator of 16-20 weight part is dissolved in the water of 600-700 weight part as material I;
(C) with in the chain-transfer agent of 6-10 weight part, the water that the 250-300 parts by weight of acrylic is dissolved in the 400-500 weight part as material II;
(D) in bed material, add pan feeding I and material II,, cool to 20-50 ℃, add the alkaline neutraliser aqueous solution 100-200 weight part of 20-50%, preferably, use the alkaline neutraliser aqueous solution 100-150 weight part of 25-35% 50-80 ℃ of reaction 1-3 hour.
9. the described method of claim 8; Expect that wherein I and the mode that material II takes to drip at the uniform velocity drip simultaneously in bed material, the control rate of addition, the dropping time of the dropping time ratio material II of feasible material I is long; Preferably, wherein expecting I and expecting that temperature remains between 55-65 ℃ in the II dropping process.
10. each described method of claim 7-9, wherein said chain-transfer agent is a thiohydracrylic acid, and preferably, said initiator is an ammonium persulphate, and more preferably said alkaline neutraliser is a sodium hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102103060A CN102731015A (en) | 2012-06-21 | 2012-06-21 | Polyester-base carboxylic acid water reducer and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102103060A CN102731015A (en) | 2012-06-21 | 2012-06-21 | Polyester-base carboxylic acid water reducer and its preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102731015A true CN102731015A (en) | 2012-10-17 |
Family
ID=46987412
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012102103060A Pending CN102731015A (en) | 2012-06-21 | 2012-06-21 | Polyester-base carboxylic acid water reducer and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102731015A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105924030A (en) * | 2016-04-29 | 2016-09-07 | 华侨大学 | Ester polycarboxylate concrete additive containing chitosan, and preparation method thereof |
| CN107337366A (en) * | 2016-12-07 | 2017-11-10 | 江苏苏博特新材料股份有限公司 | One kind sustained release collapse protection type cement water reducing agent and its preparation method and application |
| CN108193477A (en) * | 2017-12-30 | 2018-06-22 | 绍兴恒钧环保科技有限公司 | Cotton fabric enzyme oxygen, which moves back, boils drift short-flow pre-treating process |
| CN111018397A (en) * | 2019-12-02 | 2020-04-17 | 浙江天造环保科技有限公司 | High slump loss resistant type polycarboxylic acid high-performance water reducing agent and preparation method thereof |
| CN111423150A (en) * | 2020-03-03 | 2020-07-17 | 深圳市三绿科技有限公司 | Early strength water reducing agent for recycled aggregate concrete and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101955333A (en) * | 2010-10-12 | 2011-01-26 | 同济大学 | Poly carboxylic acid series water reducing agent with low content and high water-reducing rate, synthetic method and use method thereof |
-
2012
- 2012-06-21 CN CN2012102103060A patent/CN102731015A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101955333A (en) * | 2010-10-12 | 2011-01-26 | 同济大学 | Poly carboxylic acid series water reducing agent with low content and high water-reducing rate, synthetic method and use method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105924030A (en) * | 2016-04-29 | 2016-09-07 | 华侨大学 | Ester polycarboxylate concrete additive containing chitosan, and preparation 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 |
| CN107337366A (en) * | 2016-12-07 | 2017-11-10 | 江苏苏博特新材料股份有限公司 | One kind sustained release collapse protection type cement water reducing agent and its preparation method and application |
| CN107337366B (en) * | 2016-12-07 | 2019-12-27 | 江苏苏博特新材料股份有限公司 | Slow-release slump-retaining concrete water reducer and preparation method and application thereof |
| CN108193477A (en) * | 2017-12-30 | 2018-06-22 | 绍兴恒钧环保科技有限公司 | Cotton fabric enzyme oxygen, which moves back, boils drift short-flow pre-treating process |
| CN111018397A (en) * | 2019-12-02 | 2020-04-17 | 浙江天造环保科技有限公司 | High slump loss resistant type polycarboxylic acid high-performance water reducing agent and preparation method thereof |
| CN111423150A (en) * | 2020-03-03 | 2020-07-17 | 深圳市三绿科技有限公司 | Early strength water reducing agent for recycled aggregate concrete and preparation method thereof |
| CN111423150B (en) * | 2020-03-03 | 2021-09-14 | 深圳市三绿科技有限公司 | Early strength water reducing agent for recycled aggregate concrete and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1330600C (en) | Maleic acid anhydride series concrete water-reducing agent and preparation process thereof | |
| CN102718426A (en) | Modified carboxylic acid water-reducing agent and preparation method thereof | |
| CN102101758B (en) | Polyether carboxylic acid water reducer and preparation method thereof | |
| CN102731015A (en) | Polyester-base carboxylic acid water reducer and its preparation method | |
| CN102660037B (en) | Preparation method of super-sustained release ester-ether crosslinking polycarboxylic acid water reducer | |
| CN109575198B (en) | Enhanced polycarboxylate superplasticizer and preparation method thereof | |
| CN109337024B (en) | Preparation method of retarding polycarboxylate superplasticizer | |
| CN102718427B (en) | Sulfonyl modified carboxylic acid water-reducing agent and preparation method thereof | |
| CN104031216A (en) | Polyether-amide type polycarboxylic high-efficiency water reducer and preparation method thereof | |
| CN102951866B (en) | Ascorbic acid modified carboxylic water reducer and preparation method thereof | |
| CN103708760B (en) | A kind of slow-setting polycarboxylic acid water reducing agent and preparation method thereof | |
| CN102161572B (en) | Polyester type carboxylic acid series water reducing agent and preparation method thereof | |
| CN102731730A (en) | Hydrogen peroxide auxiliarily-initiated carboxylic acid water reducer and its preparation method | |
| CN102211913B (en) | Cement-based grouting material containing polyester type carboxylic acid water reducing agent and preparation method thereof | |
| CN102173638A (en) | Polycarboxylate water reducer and preparation method thereof | |
| CN108997151B (en) | Preparation method of unsaturated ester containing alkylamine group, obtained product and application | |
| CN102173635B (en) | Polycarboxylic acid high-slump-retaining zero-bleeding high-performance water reducing agent | |
| CN109942754A (en) | The method that atom transfer radical polymerization prepares retardation setting type super plasticizer | |
| CN100358825C (en) | Acrylic acid series multiple copolymer analog high efficiency water reducing agent and its synthesis method | |
| CN102086105A (en) | Modified naphthalene water reducer and preparation method thereof | |
| CN102276180B (en) | Modified melamine water reducer and preparation method thereof | |
| CN102092979B (en) | Sulfamate water-reducing agent and preparation method thereof | |
| CN101357831B (en) | Melamine modified lignosulphonate high efficiency water reducing agent, preparation method and application thereof | |
| CN113173728B (en) | Alkali-free accelerator for resisting aggregate alkali activity reaction and preparation method thereof | |
| CN113512158B (en) | Modified bio-based high-performance water reducer and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20121017 |