CN101775133B - Polyoxyethylene ether monomer, synthesis method thereof and application thereof in synthesis of water reducing agent - Google Patents
Polyoxyethylene ether monomer, synthesis method thereof and application thereof in synthesis of water reducing agent Download PDFInfo
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- CN101775133B CN101775133B CN2010101011236A CN201010101123A CN101775133B CN 101775133 B CN101775133 B CN 101775133B CN 2010101011236 A CN2010101011236 A CN 2010101011236A CN 201010101123 A CN201010101123 A CN 201010101123A CN 101775133 B CN101775133 B CN 101775133B
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Abstract
The invention provides a polyoxyethylene ether monomer which is methoxy polyethylene glycol vinyl ether formed by taking polyethylene glycol monomethyl ether as raw materials and carrying out dehydration reaction, and the structural formula is CH3O(CH2CH2O)nCH=CH2, wherein n is integer within the range of 10-44. The polyoxyethylene ether monomer reserves the advantages of the existing water reducing agent monomer compound and overcomes the defects thereof, and has better cost performance and competitive advantage. The invention also provides a preparation method of the polyoxyethylene ether monomer and the application thereof in the synthesis of the water reducing agent.
Description
Technical field
The present invention relates to a kind of polyoxyethylene ether monomer, its synthetic method and application, belong to the raw material synthesis technical field of concrete admixture.
Background technology
Polycarboxylic acid series high efficiency water reducing agent be continue with wooden calcium be the ordinary water-reducing agent of representative and with naphthalene be the high efficiency water reducing agent of representative after the third generation high efficiency water reducing agent that grows up.This class water reducer mainly is divided into two kinds of poly carboxylic acid series water reducers of ethers and ester class according to big monomeric difference, present ester class poly carboxylic acid series water reducer better performances, but cost height; Ethers poly carboxylic acid series water reducer cost is lower, but performance is poor slightly.Big monomer is a polycarboxylate water-reducer synthetic main component, and the performance and the price of water reducer had fundamental influence.Polyoxyethylene glycol that the big monomeric preparation method of traditional ester class is a methyl blocking and methacrylic acid and vinylformic acid (or its corresponding acid anhydrides) addition under the effect of catalyzer makes, owing to consumed methacrylic acid and vinylformic acid expensive raw materials such as (or its corresponding acid anhydrides), so product cost is higher; The big monomeric preparation method of ethers is by small molecules unsaturated alcohol addition of ethylene oxide such as vinyl carbinol and alkene butanols and make, be used for water reducer when synthetic, its end group characteristic performance is not as the ester class, so the water reducer performance is poor slightly, but it is less to consume expensive raw materials such as vinyl carbinol and alkene butanols when producing because of the big monomer of ethers, so cost is lower.The big monomer of this two class all has deficiency, seeks a kind of comparatively ideal substitute demand that become a reality.The invention provides the big monomeric synthetic method of a kind of new Soxylat A 25-7, be raw material promptly, issue living intramolecularly hydroxyl dehydration reaction at dehydration catalyst with the effect of being with aqua and make the methoxy poly (ethylene glycol) Vinyl Ether with the different molecular weight polyethylene glycol monomethyl ether.Because technology has been avoided methacrylic acid, vinylformic acid, vinyl carbinol, the use of expensive raw materials such as alkene butanols, and its product structure has kept the big monomeric end group characteristic of ester class, with the big monomer applications of Soxylat A 25-7 of its preparation in poly carboxylic acid series water reducer, cost is lower than the big monomer of ester class, performance is better than the big monomer of ethers, and the big monomer of this Soxylat A 25-7 is a kind of substitute preferably.
Summary of the invention
The purpose of this invention is to provide a kind of polyoxyethylene ether monomer, overcome the defective that the big monomer of ester class and the big monomer of ethers are had in the prior art simultaneously, not only with low cost but also have a better use properties.
Another order of the present invention provides a kind of preparation method of described polyoxyethylene ether monomer, makes low production cost, the technology of polyoxyethylene ether monomer reasonable and simple to operate.
A further object of the present invention provides the application of a kind of described polyoxyethylene ether monomer in the preparation cement water reducing agent.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
A kind of polyoxyethylene ether monomer is provided, and it is the methoxy poly (ethylene glycol) Vinyl Ether that is formed for the raw material dehydration reaction by poly glycol monomethyl ether, and its skeleton symbol is CH
3O (CH
2CH
2O)
nCH=CH
2, wherein n is 10～44 integer.
The molecular weight of described methoxy poly (ethylene glycol) Vinyl Ether preferred 500～2000.
The present invention also provides the preparation method of described polyoxyethylene ether monomer, may further comprise the steps:
1) be raw material with the different molecular weight polyethylene glycol monomethyl ether, itself and dehydration catalyst, band aqua and stopper are mixed with mixing solutions, wherein, by weight, described catalyst consumption is 0.1～10% of a raw material, the consumption of described band aqua is 5～10% of a raw material, and the consumption of described stopper is 0.01～0.1% of a raw material;
2) mixing solutions with the step 1) preparation issues living molecule inner dewatering reaction at 140～170 ℃, and the reaction times is 4～8 hours, promptly obtains described polyoxyethylene ether monomer.
Described dehydration catalyst can be selected from a kind of in aluminum oxide (brief note for AH), the vitriol oil, oleum or the sulphur trioxide of load phosphoric acid or phosphoric acid and vitriolic mixture; Described AH is to be that 1～10: 1 impregnation mixture gets by aluminum oxide through strong phosphoric acid or phosphoric acid and sulfuric acid mass ratio, and its consumption is preferably 2～10% of raw material weight; The consumption of the vitriol oil, oleum or sulphur trioxide is preferably 0.1～3% of raw material weight.
The preferred hexanaphthene of described band aqua.
Described stopper can be selected from a kind of in thiodiphenylamine, benzoquinones or the Resorcinol.
For reaction is carried out thoroughly, the water that forms in the reaction process is with aqua to take out of.
The present invention also provides the application of described polyoxyethylene ether monomer in the preparation cement water reducing agent, is that described polyoxyethylene ether monomer and the copolymerization of low-carbon (LC) molecule monomer are obtained polycarboxylate water-reducer.
Described application specifically is under action of evocating, described polyoxyethylene ether monomer and low-carbon (LC) molecule monomer are carried out aqueous solution copolymerization, the total consumption of wherein said low-carbon (LC) molecule monomer is 10%～30% of a polyoxyethylene ether monomer quality, described initiator amount is 0.5%～5% of all monomer total masses, polymerization temperature is controlled at 60～95 ℃, and polymerization reaction time is 3～5h.
Described low-carbon (LC) molecule monomer can be vinylformic acid, toxilic acid, maleic anhydride, methylpropene sodium sulfonate or thiohydracrylic acid etc.
Described initiator initiator system of ammonium persulfate, hydrogen peroxide or xitix.
The present invention compared with prior art has following outstanding advantage:
Compared with prior art, the present invention need not to use methacrylic acid, vinylformic acid, vinyl carbinol in preparation polyoxyethylene ether monomer process, expensive raw materials such as alkene butanols, thus reduced the production cost of polyoxyethylene ether monomer; Simultaneously, the prepared polyoxyethylene monomer structure of the present invention has kept the big monomeric end group characteristic of ester class, is used for the synthetic performance of water reducer and is better than the big monomer of ethers.Therefore, polyoxyethylene ether monomer of the present invention has kept the advantage of existing water reducer monomeric compound and has overcome its defective, has cost performance and competitive edge preferably.
Embodiment
Below raw material umber among each embodiment be weight part.
Preparation embodiment 1
200 parts of poly glycol monomethyl ethers (molecular weight is 800), 4 parts of AH, 10 parts of hexanaphthenes, Resorcinol are put into mixing in the round-bottomed flask that has prolong for 0.1 part, be warming up to 150 ± 5 ℃, reacted 6 hours, reduce to normal temperature after the reaction, remove by filter catalyzer, obtain molecular weight and be 800 polyoxyethylene ether monomer CH
3O (CH
2CH
2O)
17CH=CH
2, measuring its pair key retention rate is more than 92%.
Preparation embodiment 2
200 parts of poly glycol monomethyl ethers (molecular weight is 1200), 0.4 part of the vitriol oil, 20 parts of hexanaphthenes, Resorcinol are put into mixing in the round-bottomed flask that has prolong for 0.1 part, be warming up to 150 ± 5 ℃, reacted 6 hours, reduce to normal temperature after the reaction, obtaining the described molecular weight that obtains is 1200 polyoxyethylene ether monomer CH
3O (CH
2CH
2O)
26CH=CH
2, measuring its pair key retention rate is more than 80%.
Preparation embodiment 3
200 parts of poly glycol monomethyl ethers (molecular weight is 2000), 10% 20 parts of 10 parts of oleums, hexanaphthenes, Resorcinol are put into mixing in the round-bottomed flask that has prolong for 0.1 part, be warming up to 160 ± 5 ℃, reacted 6 hours, reduce to normal temperature after the reaction, obtain that described to obtain the described molecular weight that obtains be 2000 polyoxyethylene ether monomer CH
3O (CH
2CH
2O)
44CH=CH
2, measuring its pair key retention rate is more than 75%.
Application Example 1
To prepare the Soxylat A 25-7 that makes among the embodiment 1 is that big monomer prepares water reducer, and investigates its application performance.Concrete steps are as follows:
In round-bottomed flask, add 180 parts in end water, 70 parts of big monomers, 10 parts in vinylformic acid, 6.6 parts of maleic anhydrides, other joins ammonium persulfate solution and drips (2.5 parts of ammonium persulphates, 30 parts in water), the dropping time is 2.5 hours, temperature of reaction is 80 ± 2 ℃, reaction times is 3 hours, aging 1 hour of reaction back insulation.Insulation is cooled to below 50 ℃ after finishing, and being neutralized to the pH value with sodium hydroxide solution is 6.0-7.0, adjusts solution solid content to 20% again, promptly obtains polycarboxylic acid series high efficiency water reducing agent.Press JG/T223-2007 " high performance water reducing agent of polyocarboxy acid " and detect, recording water-reducing rate is 25%.
Application Example 2
To prepare the Soxylat A 25-7 that makes among the embodiment 2 is that big monomer prepares water reducer, and investigates its application performance.Concrete steps are as follows:
In round-bottomed flask, add 180 parts in end water, 70 parts of big monomers, 11 parts in vinylformic acid, 7 parts of maleic anhydrides, 2 parts of thiohydracrylic acids, other joins ammonium persulfate solution and drips (2.5 parts of ammonium persulphates, 30 parts in water), the dropping time is 2.5 hours, temperature of reaction is 80 ± 2 ℃, reaction times is 3 hours, aging 1 hour of reaction back insulation.Insulation is cooled to below 50 ℃ after finishing, and being neutralized to the pH value with sodium hydroxide solution is 6.0-7.0, adjusts solution solid content to 20% again, promptly obtains polycarboxylic acid series high efficiency water reducing agent.Press JG/T223-2007 " high performance water reducing agent of polyocarboxy acid " and detect, recording water-reducing rate is 26%.
Application Example 3
To prepare the Soxylat A 25-7 that makes among the embodiment 3 is that big monomer prepares water reducer, and investigates its application performance.Concrete steps are as follows:
In round-bottomed flask, add 180 parts in end water, 60 parts of big monomers, 11 parts in vinylformic acid, 7 parts of maleic anhydrides, 6 parts of methylpropene sodium sulfonates, 2 parts of thiohydracrylic acids, other joins ammonium persulfate solution and drips (2.5 parts of ammonium persulphates, 30 parts in water), the dropping time is 2.5 hours, temperature of reaction is 80 ± 2 ℃, reaction times is 3 hours, aging 1 hour of reaction back insulation.Insulation is cooled to below 50 ℃ after finishing, and being neutralized to the pH value with sodium hydroxide solution is 6.0-7.0, adjusting solution solid content to 20%, is polycarboxylic acid series high efficiency water reducing agent.Press JG/T223-2007 " high performance water reducing agent of polyocarboxy acid " and detect, recording water-reducing rate is 24%.
The present invention is not limited to the foregoing description, in actual applications, can be according to the different performance requirement of polycarboxylic acid series high efficiency water reducing agent, the polyoxyethylene ether monomer of preparation different molecular weight, select the different proportionings in the above-mentioned example, or the different proportionings except that above-mentioned each example, but all do not limit the scope of the invention in any form.
Claims (4)
1. the preparation method of a polyoxyethylene ether monomer, the skeleton symbol of described polyoxyethylene ether monomer is CH
3O (CH
2CH
2O)
nCH=CH
2, wherein n is 10～44 integer, described preparation method may further comprise the steps:
1) be raw material with the different molecular weight polyethylene glycol monomethyl ether, itself and dehydration catalyst, band aqua and stopper are mixed with mixing solutions, wherein, by weight, the consumption of described dehydration catalyst is 0.1～10% of a raw material, described band aqua is a hexanaphthene, and consumption is 5～10% of a raw material, and the consumption of described stopper is 0.01～0.1% of a raw material;
2) mixing solutions with the step 1) preparation issues living molecule inner dewatering reaction at 140～170 ℃, and the reaction times is 4～8 hours, promptly obtains described polyoxyethylene ether monomer.
2. the described preparation method of claim 1 is characterized in that: described dehydration catalyst is selected from a kind of in aluminum oxide, the vitriol oil, oleum or the sulphur trioxide of load phosphoric acid or phosphoric acid and vitriolic mixture.
3. the described preparation method of claim 2 is characterized in that: the aluminum oxide of described load phosphoric acid and vitriolic impregnation mixture is to be that 1～10: 1 impregnation mixture gets by aluminum oxide through phosphoric acid and sulfuric acid mass ratio, and consumption is 2～10% of a raw material weight.
4. the described preparation method of claim 1 is characterized in that: described stopper is selected from a kind of in thiodiphenylamine, benzoquinones or the Resorcinol.
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| CN102140166B (en) * | 2010-11-24 | 2013-07-17 | 辽宁奥克化学股份有限公司 | Unsaturated polyether as well as preparation method and application thereof |
| CN103897115B (en) * | 2012-12-26 | 2017-02-08 | 辽宁奥克化学股份有限公司 | Terpolymer as concrete workability improver |
| CN104230202B (en) * | 2014-09-02 | 2016-03-09 | 科之杰新材料集团有限公司 | A kind of cement water reducing agent methoxy group normal olefine polyether monomer and preparation method thereof |
| CN106084149A (en) * | 2016-06-08 | 2016-11-09 | 柳州市强威锻造厂 | A kind of phthalic acid class polycarboxylate water-reducer |
| CN106084148A (en) * | 2016-06-08 | 2016-11-09 | 柳州市强威锻造厂 | A kind of maleic acid class polycarboxylate water-reducer |
| CN108821634B (en) * | 2018-08-17 | 2020-10-23 | 阳泉市高星建材外加剂有限公司 | High-efficiency concrete water reducing agent and preparation method thereof |
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