CN101792527B - Polyoxyethylene ether-ester type monomer, synthesis thereof and application in synthesis of water reducing agent - Google Patents

Polyoxyethylene ether-ester type monomer, synthesis thereof and application in synthesis of water reducing agent Download PDF

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CN101792527B
CN101792527B CN2010101028951A CN201010102895A CN101792527B CN 101792527 B CN101792527 B CN 101792527B CN 2010101028951 A CN2010101028951 A CN 2010101028951A CN 201010102895 A CN201010102895 A CN 201010102895A CN 101792527 B CN101792527 B CN 101792527B
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ester type
polyoxyethylene ether
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acid
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CN101792527A (en
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朱建民
刘兆滨
仲崇纲
董振鹏
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LIAONING OXIRANCHEM GROUP CO Ltd
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Abstract

The invention provides a polyoxyethylene ether-ester type monomer, which is a double-bonded ester compound formed by leading MPEG with the molecular weight of 1000-1200 to carry out hydroxy-terminated oxidation for generating methoxy polyoxyethylene acetate, and further carrying out esterization with enol, and the structural formula is as follows: CH3O(CH2CH2O)nCH2COOCH2RCR' = CR'', wherein n is an integral number from 10 to 44; R is (CH2)m, wherein m is the integral number from 0 to 2; R' is H or CH3; and R'' is H2, CH3 or CH2CH3. The polyoxyethylene ether-ester type monomer has high purity and can carry out water solution copolymerization with olefin acid (or olefin anhydride) with low carbon molecules, olefin sulfonate acid and salts thereof and other small monomers, and a synthesized water reducing agent has better water reducing performance.

Description

A kind of polyoxyethylene ether-ester type monomer, its synthetic application that reaches in water reducer is synthetic
Technical field
The present invention relates to a kind of polyoxyethylene ether-ester type monomer and synthetic and application thereof, belong to the technical field of concrete admixture.
Background technology
Usually polyoxyethylene ether-ester type monomer one is to be got with (or its acid anhydrides) esterification of low carbon enoic acid by methoxy poly (ethylene glycol) (MPEG); The 2nd, carry out transesterification reaction and get by MPEG and low carbon enoic acid ester.Be applied to the synthetic of cement water reducing agent as the polymeric main raw material.Report in this regard is of common occurrence both at home and abroad, and as CN 1316398A and US6, domestic and international patent such as 362,364 grades describes the synthesis technique of this carboxylate in detail.What patent CN 1316398A was adopted is ester exchange process, patent US6,362,364 what adopted is the alkyd condensation process, because the raw material that these two kinds of technologies are adopted is respectively low carbon enoic acid (or its acid anhydrides) and low carbon enoic acid ester, their polymerization activity is all stronger, so even if used stopper also to be difficult to avoid the generation of polymerization side reactions in esterification process.The performance of too much stopper and polymeric by-products all can synthesizing to the water reducer of polyoxyethylene ether-ester type monomer causes negative impact in various degree.At this problem, the present invention proposes a kind of synthetic method of new polyoxyethylene ether-ester type monomer, promptly at first MPEG is carried out the terminal hydroxy group oxidation and synthesizes corresponding methoxy polyoxyethylene acetate, thereby and then the low-carbon (LC) enol that itself and polymerization activity is relatively low carry out esterification and obtain a kind of novel polyoxyethylene ether-ester type monomer.Because the polymerization activity of low-carbon (LC) enol generally is lower than low carbon enoic acid (or its acid anhydrides) and low carbon enoic acid ester, so in esterification process, reduced the generation of the add-on and the polymerization side reactions of stopper effectively, fundamentally improved the synthetic performance of water reducer of polyoxyethylene ether-ester type monomer.
Summary of the invention
The objective of the invention is to: a kind of polyoxyethylene ether-ester type monomer is provided, has the synthetic performance of better water reducer.
Another object of the present invention is: a kind of synthetic method of described polyoxyethylene ether-ester type monomer is provided, has reduced the usage quantity of stopper and the growing amount of polymeric by-products effectively.
A further object of the present invention is: the application of described polyoxyethylene ether-ester type monomer in synthetic water reducer is provided.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
A kind of polyoxyethylene ether-ester type monomer is provided, and it is, and to be 1000~1200 MPEG by molecular weight issue after the hydroxyl oxidize of causing trouble generates methoxy polyoxyethylene acetate in the oxygenant effect, the carboxylate of the two keys of band that obtain with the enol esterification again, and its structural formula is: CH 3O (CH 2CH 2O) nCH 2COOCH 2RCR '=CR ", wherein, n is 10~44 integer; R is (CH 2) m, wherein m is 0~2 integer; R ' is H or CH 3R " is H 2, CH 3Or CH 2CH 3
Described oxygenant can be sodium dichromate 99 and vitriolic mixed aqueous solution, or chromium trioxide and vitriolic mixed aqueous solution.
The preferred low-carbon (LC) enol of described enol, further preferred vinylcarbinol, butenol, pentenol or methyl butene alcohol etc.
The present invention also provides the preparation method of described polyoxyethylene ether-ester type monomer, may further comprise the steps:
1) preparation of methoxy polyoxyethylene acetate: in the presence of oxygenant, the heating molecular weight is 1000~1200 MPEG, make it that terminal hydroxy group oxidizing reaction take place, described oxygenant consumption is 40%~100% of a MPEG weight, control reaction temperature is at 80~110 ℃, reacted 1.5~2 hours, product filters through neutralization and obtains methoxy polyoxyethylene acetate;
2) preparation of polyoxyethylene ether-ester type monomer: the methoxy polyoxyethylene acetate that step 1) is obtained and the stopper of MPEG quality 0.6 ‰~2.5 ‰, the catalyzer of MPEG quality 1%~5%, the band aqua of MPEG quality 5%~20% and the low-carbon (LC) enol of MPEG quality 6%~18% heat altogether carry out esterification, temperature is controlled at 80~150 ℃, reacted 6~10 hours, the water that constantly divides the de-esterifying process to take out of therebetween, make esterification near complete, boil off the band aqua at last, reaction obtains methoxy polyoxyethylene acetate low-carbon (LC) enol ester after finishing, be described polyoxyethylene ether-ester type monomer, structure is as follows:
CH 3O(CH 2CH 2O) nCH 2COOCH 2RCR′=CR″
Wherein, n is 10~44 integer; R is (CH 2) m, wherein m is 0~2 integer; R ' is H or CH 3R " is H 2, CH 3Or CH 2CH 3
Oxygenant described in the step 1) can be sodium dichromate 99 and vitriolic mixed aqueous solution, or chromium trioxide and vitriolic mixed aqueous solution;
Step 2) the band aqua described in can be selected hexanaphthene; Described stopper can be thiodiphenylamine or Resorcinol; Described catalyzer can be a tosic acid; Described low-carbon (LC) enol can be vinylcarbinol, butenol, pentenol or methyl butene alcohol etc.
The present invention also provides the application of described polyoxyethylene ether-ester type monomer in water reducer is synthetic, is under action of evocating, carries out aqueous solution copolymerization with described polyoxyethylene ether-ester type monomer and low-carbon (LC) molecule monomer, synthetic water reducer.
In the described application, described low-carbon (LC) molecule monomer consumption is preferably 10%~30% of described polyoxyethylene ether-ester type monomer quality, the consumption of described initiator is preferably 0.5%~5% of all monomer total masses, and polymerization temperature is controlled at 60~95 ℃, and the reaction times is 2-6 hour.
Minor comonomers such as the olefin(e) acid that described low-carbon (LC) molecule monomer can be the low-carbon (LC) molecule or its acid anhydrides, alkene sulfonic acid or its esters, the mixture of one or more in preferred vinylformic acid, methacrylic acid, toxilic acid, maleic anhydride, methacrylic sulfonic acid, vinyl sulfonic acid, styrene sulfonic acid, 2-acrylamide-2-methacrylic sulfonic acid and the salt thereof.
Described initiator can be a kind of in ammonium persulphate, Potassium Persulphate, the azo-bis-isobutyrate hydrochloride.
The preparation process of polyoxyethylene ether-ester type monomer of the present invention is at first the oxidation of MPEG terminal hydroxy group to be generated methoxy polyoxyethylene acetate, and then obtains the carboxylate of the two keys of different bands with the esterification of various low-carbon (LC) enol.Compared with prior art, beneficial effect of the present invention is:
1. the monomer esterification yield height, the purity height that prepare.
On the one hand, preparation method of the present invention can reduce the usage quantity of stopper effectively, the usage quantity of stopper is generally more than 5 ‰ of MPEG weight among the preparation method of prior art, and the amount of application of stopper only is 0.6 ‰ of MPEG weight~2.5 ‰ among the preparation method of the present invention, owing to not reacting, the stopper that adds in the monomer preparation do not residue in the monomer that makes, not only have influence on the purity of monomer product, and can be to next step polymerization of monomer, promptly the polyreaction of further synthetic water reducer impacts, therefore the remarkable reduction of stopper consumption among the preparation method of the present invention, not only make the monomer product purity that makes thus improve, and when preparing water reducer with this monomer product, the influence of the stopper that polyreaction is suffered will inevitably significantly reduce.
On the other hand, method of the present invention can also reduce the growing amount of polymeric by-products in the monomer preparation, this is when improving esterification yield, also made contribution for significantly improving product purity, preparation method's of the present invention esterification yield can reach more than 97%, and the big monomer esterification yield of prior art is all below 96%.
2. and preparation method's of the present invention entire reaction operation simple and feasible, realize suitability for industrialized production easily.When thus obtained polyoxyethylene ether-ester type monomer was used for synthesizing water reducer, the water reducer that obtains was better than the water reducer performance of prior art.
Embodiment
It is synthetic that polyoxyethylene ether-ester type monomer of the present invention was divided into for two steps, and the first step is that the methoxy poly (ethylene glycol) monomethyl ether is oxidized to methoxy polyoxyethylene acetate; Second step was carried out esterification with methoxy polyoxyethylene acetate and low-carbon (LC) enol under catalyzer and stopper effect, obtain methoxy polyoxyethylene acetate low-carbon (LC) enol ester.Describe synthetic method of the present invention in detail with oxidizing reaction and esterification below.
1) oxidizing reaction:
At first MPEG is oxidized to methoxy polyoxyethylene acetate, preparation methoxy polyoxyethylene acetate then will be under the oxygenant effect, a certain amount of MPEG joins in the four-hole bottle that has stirring, heating, treat that MPEG melts fully after, start to stir, continue heating, control reaction temperature is reacted after 1.5~2 hours at 80~110 ℃, and product filters through neutralization and obtains methoxy polyoxyethylene acetate.
2) esterification:
Add in the lump in the reaction flask of being furnished with water trap obtaining oxidation products methoxy polyoxyethylene acetate and stopper, catalyzer and band aqua, add the low-carbon (LC) enol simultaneously, start and stir, esterification is carried out in heating, reacted 6~10 hours, the water that constantly divides the de-esterifying process to take out of makes esterification near complete, thereby obtains ester methoxy polyoxyethylene acetate low-carbon (LC) enol ester therebetween.
Below with molecular weight be respectively 1000 and 1200 MPEG be example the present invention will be further described, but the present invention is not limited only to these examples.Also can fully understand essence of an invention and invention scope by these embodiment, further understand the present invention.
Embodiment 1
Stirring is housed, temperature is taken into account in the 500ml four-hole boiling flask of water trap, add MPEG (molecular weight 1000) 125g, sodium dichromate 99 and vitriolic mixed aqueous solution 100g (sodium dichromate 99 24g wherein, sulfuric acid 35.9g, water 40.1g), start stirring and be heated to 100 ℃, react after 2 hours, be cooled to 50 ℃, slowly splash into the sodium hydroxide solution of 18.33g 40%, the elimination precipitation obtains methoxy polyoxyethylene acetate clear liquid.Then methoxy polyoxyethylene acetate clear liquid is added in the 500ml four-hole boiling flask, add hydroquinone of polymerization retarder 0.31g, vinylcarbinol 8.75g, add catalyzer tosic acid 2g and hexanaphthene 17g, heating starting stirs and maintains the temperature at 82 ℃, the continuous water that divides the de-esterifying process to take out of, react and obtained methoxy polyoxyethylene acetate propylene alcohol ester in 9 hours, be a kind of of described polyoxyethylene ether-ester type monomer, its structural formula is: CH 3O (CH 2CH 2O) 21CH 2COOCH 2CH=CH 2, esterification yield is 97.8%.
Embodiment 2
Stirring is housed, temperature is taken into account in the 500ml four-hole boiling flask of water trap, add MPEG (molecular weight 1000) 125g, sodium dichromate 99 and vitriolic mixed aqueous solution 100g (sodium dichromate 99 24g wherein, sulfuric acid 35.9g, water 40.1g), heating, start and stir, keep 110 ℃ of still temperature, react after 1.5 hours, be cooled to 50 ℃, slowly splash into the sodium hydroxide solution of 18.33g 40%, the elimination precipitation obtains methoxy polyoxyethylene acetate clear liquid.Then methoxy polyoxyethylene acetate clear liquid is added in the 500ml four-hole boiling flask, add hydroquinone of polymerization retarder 0.11g, butenol 18.75g, add catalyzer tosic acid 5g and hexanaphthene 25g, heating starting stirs and maintains the temperature at about 100 ℃, the continuous water that divides the de-esterifying process to take out of, react and obtained methoxy polyoxyethylene acetate butylene alcohol ester in 8 hours, be a kind of of described polyoxyethylene ether-ester type monomer, its structural formula is: CH 3O (CH 2CH 2O) 21CH 2COOCH 2CH 2CH=CH 2, esterification yield is 98.5%.
Embodiment 3
Stirring is housed, temperature is taken into account in the 500ml four-hole boiling flask of water trap, add MPEG (molecular weight 1200) 150g, chromium trioxide and vitriolic mixed aqueous solution 65g (chromium trioxide 65.12g wherein, sulfuric acid 5g, water 19.66g), heating, start and stir, keep 110 ℃ of still temperature, react after 2 hours, be cooled to 50 ℃, slowly splash into the sodium hydroxide solution of 18.33g 40%, the elimination precipitation obtains methoxy polyoxyethylene acetate clear liquid.Then methoxy polyoxyethylene acetate clear liquid is added in the 500ml four-hole boiling flask, add hydroquinone of polymerization retarder 0.12g, methyl butene alcohol 19.25g, add catalyzer tosic acid 4g and hexanaphthene 22g, heating starting stirs and maintains the temperature at about 120 ℃, the continuous water that divides the de-esterifying process to take out of, react and obtained methoxy polyoxyethylene acetate methyl butene alcohol ester in 9 hours, be a kind of of described polyoxyethylene ether-ester type monomer, its structural formula is: CH 3O (CH 2CH 2O) 26CH 2COOCH 2CH (CH 3) CH=CH 2, esterification yield is 98.0%.
Polyoxyethylene ether-ester type monomer of the present invention can be used as a kind of monomer, is used for the synthetic macromolecule tensio-active agent, as water reducer, static inhibitor, thickening material, emulsifying agent and emulsion splitter etc., is specially adapted to synthetic cement water reducing agent.The method of synthetic water reducer is that the minor comonomers such as olefin(e) acid (or olefin(e) acid acid anhydride), alkene sulfonic acid and its esters with described methoxy polyoxyethylene acetate low-carbon (LC) enol ester and low-carbon (LC) molecule are made into the aqueous solution, control end water is at 60~95 ℃, drip monomer solution and initiator solution simultaneously, drip in 2~4 hours, monomer solution will drip prior to initiator solution, being incubated 1~2 hour makes polyreaction complete, lowering the temperature and mixing up PH promptly obtains corresponding water reducer to neutrality, concrete synthetic see embodiment 4 and embodiment 5.
Embodiment 4
Add end water 200g in the there-necked flask of 1000mL, ester 125.5g, methacrylic acid 29.3g, thiohydracrylic acid 0.913g and the 84.82g deionized water of example 2 gained are mixed, drip off in 3 hours when treating that the deionized water temperature reaches 90 ℃ in the flask, drip the initiator solution of 1.73g ammonium persulphate and 30g deionized water simultaneously, the initiator solution dropping time is 4 hours.Agent solution to be triggered dropwises and starts from 90 ℃ of insulations 1 hour, be cooled to 50 ℃, being neutralized to PH with 30% sodium hydroxide solution is 6.0~7.0, obtain solid content and be 35% polycarboxylic acid series high efficiency water reducing agent, press JG/T223-2007 " high performance water reducing agent of polyocarboxy acid " and detect, its water-reducing rate is more than 30%.
Embodiment 5
Add end water 268g in the there-necked flask of 1000mL, ester 146g, vinylformic acid 24.3g, thiohydracrylic acid 0.946g and the 84.82g deionized water of example 3 gained are mixed, drip off in 3 hours when treating that the deionized water temperature reaches 90 ℃ in the flask, drip the initiator solution of 1.78g ammonium persulphate and 30g deionized water simultaneously, the initiator solution dropping time is 4 hours.Agent solution to be triggered dropwises and starts from 90 ℃ of insulations 1 hour, be cooled to 50 ℃, being neutralized to PH with 30% sodium hydroxide solution is 6.0~7.0, obtain solid content and be 30% polycarboxylic acid series high efficiency water reducing agent, press JG/T223-2007 " high performance water reducing agent of polyocarboxy acid " and detect, its water-reducing rate is more than 28%.

Claims (10)

1. polyoxyethylene ether-ester type monomer, it is characterized in that: it is to be that the MPEG of 1000-1200 issues after the hydroxyl oxidize of causing trouble generates methoxy polyoxyethylene acetate in the oxygenant effect by molecular weight, the carboxylate of the two keys of the band that obtains with the enol esterification again, its structural formula is as follows
CH 3O(CH 2CH 2O) nCH 2COOCH 2RCR′=CR″
Wherein n is 10~44 integer; R is (CH 2) m, wherein m is 0~2 integer; R ' is H or CH 3R " is H 2
2. the described polyoxyethylene ether-ester type monomer of claim 1, it is characterized in that: described oxygenant is sodium dichromate 99 and vitriolic mixed aqueous solution, or chromium trioxide and vitriolic mixed aqueous solution; Described enol is the low-carbon (LC) enol.
3. the described polyoxyethylene ether-ester type monomer of claim 2 is characterized in that: described low-carbon (LC) enol is selected from a kind of in vinylcarbinol, butenol or the pentenol.
4. the preparation method of the described polyoxyethylene ether-ester type monomer of claim 1 may further comprise the steps:
1) preparation of methoxy polyoxyethylene acetate: in the presence of oxygenant, the heating molecular weight is 1000~1200 MPEG generation terminal hydroxy group oxidizing reaction, described oxygenant consumption is 40%~100% of a MPEG weight, control reaction temperature is at 80~110 ℃, reacted 1.5~2 hours, product filters through neutralization and obtains methoxy polyoxyethylene acetate;
2) preparation of polyoxyethylene ether-ester type monomer: the methoxy polyoxyethylene acetate that step 1) is obtained and the stopper of MPEG quality 0.6 ‰~2.5 ‰, the catalyzer of MPEG quality 1%~5%, the band aqua of MPEG quality 5%~20% and the low-carbon (LC) enol of MPEG quality 6%~18% heat altogether carry out esterification, temperature is controlled at 80~150 ℃, reacted 6~10 hours, the water that constantly divides the de-esterifying process to take out of therebetween, make esterification near complete, boil off the band aqua at last, reaction obtains methoxy polyoxyethylene acetate low-carbon (LC) enol ester after finishing, be described polyoxyethylene ether-ester type monomer, structure is as follows:
CH 3O(CH 2CH 2O) nCH 2COOCH 2RCR′=CR″
Wherein, n is 10~44 integer; R is (CH 2) m, wherein m is 0~2 integer; R ' is H or CH 3R " is H 2
5. the preparation method of the described polyoxyethylene ether-ester type monomer of claim 4, it is characterized in that: the oxygenant described in the step 1) is sodium dichromate 99 and vitriolic mixed aqueous solution, or chromium trioxide and vitriolic mixed aqueous solution.
6. the preparation method of the described polyoxyethylene ether-ester type monomer of claim 4 is characterized in that: step 2) described in the band aqua be hexanaphthene; Described stopper is thiodiphenylamine or Resorcinol; Described catalyzer is a tosic acid; Described low-carbon (LC) enol is vinylcarbinol, butenol or pentenol.
7. the application of the described polyoxyethylene ether-ester type monomer of claim 1 in water reducer is synthetic is under action of evocating, carries out aqueous solution copolymerization with described polyoxyethylene ether-ester type monomer and low-carbon (LC) molecule monomer, synthetic water reducer; Described low-carbon (LC) molecule monomer consumption is 10%~30% of a described polyoxyethylene ether-ester type monomer quality, and the consumption of described initiator is 0.5%~5% of all monomer total masses, and polymerization temperature is controlled at 60~95 ℃.
8. the described application of claim 7 is characterized in that: the olefin(e) acid that described low-carbon (LC) molecule monomer is the low-carbon (LC) molecule or its acid anhydrides, alkene sulfonic acid or its esters.
9. the described application of claim 7 is characterized in that: described low-carbon (LC) molecule monomer is selected from one or more the mixture in vinylformic acid, methacrylic acid, toxilic acid, maleic anhydride, methacrylic sulfonic acid, vinyl sulfonic acid, styrene sulfonic acid, 2-acrylamide-2-methacrylic sulfonic acid or its salt.
10. the described application of claim 7 is characterized in that: described initiator is selected from a kind of in ammonium persulphate, Potassium Persulphate or the azo-bis-isobutyrate hydrochloride.
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