CN103980437B - A kind of poly carboxylic acid series water reducer and preparation method thereof - Google Patents

A kind of poly carboxylic acid series water reducer and preparation method thereof Download PDF

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CN103980437B
CN103980437B CN201410228501.5A CN201410228501A CN103980437B CN 103980437 B CN103980437 B CN 103980437B CN 201410228501 A CN201410228501 A CN 201410228501A CN 103980437 B CN103980437 B CN 103980437B
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allyl
carboxylic acid
poly carboxylic
water reducer
water
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CN103980437A (en
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孙永强
杨卉艳
郭建国
史修启
智丽飞
孙晋源
张勇
武华萍
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China Daily Chemical Industry Research Institute
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China Daily Chemical Industry Research Institute
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Abstract

A kind of poly carboxylic acid series water reducer molecular formula is as follows:R in formula1For straight chain that carbon number is 6 18 and branched alkyl;0≤a≤30;0≤b≤30;0≤x≤30;0≤y≤30, wherein a and b can not be zero simultaneously, x and y can not be zero simultaneously.The present invention has that preparation technology is simple, reaction condition is gentle, and technical process is easily controllable.Properties of product are stable, the advantage that water-reducing effect is good.

Description

A kind of poly carboxylic acid series water reducer and preparation method thereof
Technical field
The invention belongs to a kind of water reducer and preparation method, be specifically related to a kind of poly carboxylic acid series water reducer and Preparation method.
Technical background
After concrete mixes water reducer, owing to Water-reducing Admixtures To Cements granule has sufficient peptizaiton, thus Improve the mobility of concrete, enhance its workability;In the case of keeping original workability, can To reduce water consumption, improve the intensity of concrete.Due to the application of water reducer, its water-reduction is permissible It is substantially reduced the ratio of mud of concrete, thus improves the intensity of concrete, in this manner it is possible to make more The concrete of high intensity grade, in the case of ad eundem, it is possible to reduce cement consumption, thus reduces into This, increase economic efficiency.
In recent years, along with increasing and the fast development of high ferro of China's building, polycarboxylate water-reducer was with it The outstanding advantages such as water-reducing rate is high, concrete retentivity is good, have obtained extensively in the field such as railway, traffic Application.On domestic market, poly carboxylic acid series water reducer is essentially divided into two big classes: a class is ether type, with horse Carrying out anhydride with allyl polyglycol is the copolymer of formant;One class is ester type, with (methyl) third Olefin(e) acid and methoxy poly (ethylene glycol) (methyl) acrylate are the copolymer of essential building blocks.City at present On field water reducer to prepare raw material variety varied, mainly have MPEG series, APEG series, Yi Jixin The modified polyether TPEG series developed.But above two water reducer molecule does not all contain chain alkyl, Not easily pass through change carbon chain lengths and reach the purpose of MOLECULE DESIGN.Use pi-allyl fatty alcohol ether alkoxylate Thing and allyl alcohol alcoxylates are raw material to carry out copolymerization with methacrylic acid and prepares polycarboxylic-acid diminishing Agent, does not finds report through retrieval.
Summary of the invention
It is an object of the invention to provide a kind of MOLECULE DESIGN that polycarboxylate water-reducer is carried out, employing pi-allyl Fatty alcohol ether alcoxylates and allyl alcohol alcoxylates are that raw material carries out copolymerization system with methacrylic acid Standby poly carboxylic acid series water reducer and preparation method thereof.
This method uses pi-allyl fatty alcohol ether alcoxylates and allyl alcohol alcoxylates to be raw material Copolymerization is carried out, by regulating the fatty chain length of pi-allyl fatty alcohol ether alcoxylates with methacrylic acid And ethyoxyl or the degree of polymerization of propoxyl group, it is possible to achieve polycarboxylate water-reducer is carried out MOLECULE DESIGN, improves Its application performance.
The reaction equation of the present invention is as follows:
R in formula1For straight chain that carbon number is 6-18 and branched alkyl;0≤a≤30;0≤b≤30.0≤x≤30; 0≤y≤30, wherein a and b can not be zero simultaneously, x and y can not be zero simultaneously.
The polycarboxylate water-reducer that the present invention provides, its molecular formula is as follows:
R in formula1For straight chain that carbon number is 6-18 and branched alkyl;0≤a≤30;0≤b≤30;0≤x≤30; 0≤y≤30, wherein a and b can not be zero simultaneously, x and y can not be zero simultaneously.
Preparation method of the present invention comprises the following steps:
(1) water, pi-allyl fatty alcohol ether alcoxylates, allyl alcohol alkoxyl are added in the reactor Compound and oxidant, be heated with stirring to 30-70 DEG C, wherein pi-allyl fatty alcohol ether alcoxylates and water Mass ratio is 1:1~3, pi-allyl fatty alcohol ether alcoxylates and the mass ratio of allyl alcohol alcoxylates For 1:2~3, oxidizer is the 0.1~2wt% of pi-allyl fatty alcohol ether alcoxylates;
(2) it is 1:3~6 by pi-allyl fatty alcohol ether alcoxylates and methacrylic acid mol ratio, by first The mixed aqueous solution of base acrylic acid and reducing agent is added dropwise in step (1) reaction, and time for adding is 2~3 little Time, wherein methacrylic acid is 1:1~3 with the mass ratio of water, and reducing agent consumption is the 0.1~2 of methacrylic acid Wt%;
3) dropwise reaction terminates, and is incubated 1 hour, is down to less than 25 DEG C, adds aqueous slkali regulation pH Value, to neutrality, discharging, had both obtained described polycarboxylate water-reducer.
Oxidant as above is the one in persulfate or hydrogen peroxide.
Reducing agent as above is the one in sodium sulfite or sodium pyrosulfite.
Aqueous slkali as above includes the one in sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate, Its concentration is between 5~50wt%.
Advantages of the present invention is as follows:
1, all not containing long-chain in general water reducer molecule, the present invention can be by putting into the alkene of different carbon chain Propyl group fatty alcohol ether alcoxylates, as raw material, obtains the polycarboxylate water-reducer of different carbon chain, permissible Reach by the degree of polymerization changing carbon chain lengths and ethyoxyl or propoxyl group, molecule to be designed so that it is should In different types of water reducer.
2, the preparation technology of the present invention is simple, reaction condition is gentle, and technical process is easily controllable.
3, properties of product are stable, and water-reducing effect is good, and the technology being suitable for modern high performance concrete requires and executes Work requirement.
Detailed description of the invention
Embodiment 1:
Addition deionized water 150 grams in four-hole bottle, pi-allyl hexanol polyoxyethylene ether (30EO) 150 grams, Allyl alcohol ethoxylate (30EO) 300 grams, sodium peroxydisulfate 0.15 gram, it is heated with stirring to 70 DEG C, Start to drip the aqueous solution of methacrylic acid and sodium sulfite, wherein 53 grams of (n allyls of methacrylic acid Base hexanol polyoxyethylene ether: n methacrylic acid=1:6), sodium sulfite 0.05 gram, 60 grams of water, 2 Completion of dropwise addition after hour, is cooled to 20 DEG C after being incubated 1 hour in 70 DEG C, adds the sodium hydroxide of 5wt% Solution regulation pH value, to neutral, obtains following structure water reducer:
Embodiment 2:
Addition deionized water 240 grams in four-hole bottle, pi-allyl octadecanol polyethenoxy ether (8EO) 80 grams, Allyl alcohol block copolymer (9EO-5PO) 240 grams, sodium peroxydisulfate 1.6 grams, it is heated with stirring to 30 DEG C, Start to drip the aqueous solution of methacrylic acid and sodium pyrosulfite, wherein 31 grams of (n allyls of methacrylic acid Base octadecanol polyethenoxy ether: n methacrylic acid=1:3), sodium pyrosulfite 0.62 gram, 93 grams of water, Completion of dropwise addition after 3 hours, is cooled to 20 DEG C after being incubated 1 hour in 30 DEG C, adds the potassium hydroxide of 50% Solution regulation pH value, to neutral, obtains following structure water reducer:
Embodiment 3:
Deionized water 160 grams, the ethoxylated propoxylated copolymerization of pi-allyl lauryl alcohol ether is added in four-hole bottle Thing (12EO-5PO) 80 grams, allyl alcohol propoxylate (12EO) 180 grams, potassium peroxydisulfate 0.8 Gram, it is heated with stirring to 60 DEG C, starts to drip the aqueous solution of methacrylic acid and sodium sulfite, Qi Zhongjia 20 grams of base acrylic acid (the ethoxylated propoxylated polymers that takes altogether of n pi-allyl lauryl alcohol ether: n metering system Acid=1:5), sodium sulfite 0.2 gram, 50 grams of water, completion of dropwise addition after 2 hours, it is incubated 1 in 60 DEG C It is cooled to 20 DEG C after hour, adds the sodium carbonate liquor regulation pH value extremely neutrality of 15%, obtain following knot Structure water reducer:
Embodiment 4:
Deionized water 150 grams, pi-allyl isooctanol polyethoxylate (20EO) 100 is added in four-hole bottle Gram, allyl alcohol ethoxylate (20EO) 250 grams, hydrogen peroxide 1.5 grams, it is heated with stirring to 50 DEG C, Start to drip methacrylic acid and the aqueous solution of pyrosulfurous acid hydrogen sodium, wherein 33 grams of (n alkene of methacrylic acid Propyl group isooctanol polyethoxylate: n methacrylic acid=1:4), sodium sulfite 1 gram, 70 grams of water, Completion of dropwise addition after 2.5 hours, is cooled to 20 DEG C after being incubated 1 hour in 50 DEG C, adds the sodium carbonate of 25% Solution regulation pH value, to neutral, obtains following structure water reducer:
Above-described embodiment prepares the performance test results such as following table of sample:
Concrete water-reducing ratio and compressive strength test are entered with reference to GB 8,076 1997 " concrete admixture " OK.Pi-allyl ether type polycarboxylic acid series dehydragent PC-A is the most common employing allyl polyglycol (APEG), maleic anhydride and acrylic acid methyl ester. are the poly carboxylic acid series water reducer of monomer synthesis.

Claims (5)

1. a poly carboxylic acid series water reducer, it is characterised in that its molecular formula is as follows:
R in formula1For straight chain that carbon number is 6-18 and branched alkyl;0≤a≤30;0≤b≤30;0≤x≤30; 0≤y≤30, wherein a and b can not be zero simultaneously, x and y can not be zero simultaneously.
The preparation method of a kind of poly carboxylic acid series water reducer the most as claimed in claim 1, it is characterised in that include following Step:
(1) water, pi-allyl fatty alcohol ether alcoxylates, allyl alcohol alkoxylate are added in the reactor Thing and oxidant, be heated with stirring to 30-70 DEG C, wherein pi-allyl fatty alcohol ether alcoxylates and the quality of water Ratio is 1:1~3, and pi-allyl fatty alcohol ether alcoxylates with the mass ratio of allyl alcohol alcoxylates is 1:2~3, oxidizer is the 0.1~2wt% of pi-allyl fatty alcohol ether alcoxylates;
(2) it is 1:3~6 by pi-allyl fatty alcohol ether alcoxylates and methacrylic acid mol ratio, by methyl The mixed aqueous solution of acrylic acid and reducing agent is added dropwise to reaction in step (1), and time for adding is 2~3 hours, Wherein methacrylic acid is 1:1~3 with the mass ratio of water, and reducing agent consumption is the 0.1~2wt% of methacrylic acid;
(3) dropwise reaction terminates, and is incubated 1 hour, is down to less than 25 DEG C, adds aqueous slkali regulation pH value To neutral, discharging, obtain described polycarboxylate water-reducer.
The preparation method of a kind of poly carboxylic acid series water reducer the most as claimed in claim 2, it is characterised in that described oxygen Agent is the one in persulfate or hydrogen peroxide.
The preparation method of a kind of poly carboxylic acid series water reducer the most as claimed in claim 2, it is characterised in that described goes back Former dose is the one in sodium sulfite or sodium pyrosulfite.
The preparation method of a kind of poly carboxylic acid series water reducer the most as claimed in claim 2, it is characterised in that described alkali Solution includes the one in sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate, and its concentration is 5~50wt% Between.
CN201410228501.5A 2014-05-28 2014-05-28 A kind of poly carboxylic acid series water reducer and preparation method thereof Active CN103980437B (en)

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CN109535341A (en) * 2018-11-16 2019-03-29 中交二航武汉港湾新材料有限公司 Hydrophobically modified viscosity reduction type polycarboxylate water-reducer and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102199298A (en) * 2011-03-23 2011-09-28 中国日用化学工业研究院 Preparation method for polycarboxylic acid series comb-shaped surface active agent
CN102503221A (en) * 2011-08-12 2012-06-20 周绍春 Cyclohexanol grafted polycarboxylic acid water reducing agent and preparation method thereof
CN102585194A (en) * 2011-12-14 2012-07-18 中国日用化学工业研究院 Method for synthesizing allyl fatty alcohol-polyoxyethylene ether or allyl alkylphenol ethoxylate

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102199298A (en) * 2011-03-23 2011-09-28 中国日用化学工业研究院 Preparation method for polycarboxylic acid series comb-shaped surface active agent
CN102503221A (en) * 2011-08-12 2012-06-20 周绍春 Cyclohexanol grafted polycarboxylic acid water reducing agent and preparation method thereof
CN102585194A (en) * 2011-12-14 2012-07-18 中国日用化学工业研究院 Method for synthesizing allyl fatty alcohol-polyoxyethylene ether or allyl alkylphenol ethoxylate

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