CN105273180A - Synthesis method of unsaturated polyoxyethylene ether derivative and product of unsaturated polyoxyethylene ether derivative - Google Patents
Synthesis method of unsaturated polyoxyethylene ether derivative and product of unsaturated polyoxyethylene ether derivative Download PDFInfo
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Abstract
The invention provides a synthesis method of an unsaturated polyoxyethylene ether derivative. According to the method, an alkenyl phenol compound is used as an initial raw material is subjected to halogen substituting reaction with halogen gas; the obtained halogen substituted alkenyl phenol compound A and ammonia gas are subjected to substituting reaction with to produce an amino-substituted alkenyl phenol compound B; finally, the amino-substituted alkenyl phenol compound B and EO (ethylene oxide) or PO (propylene oxide) complete a polymerization reaction to obtain a target product. The invention also provides the unsaturated polyoxyethylene ether derivative prepared by using the method. The unsaturated polyoxyethylene ether derivative can be used for preparing polycarboxylate superplasticizers, so that polycarboxylate superplasticizers have excellent early strength effects; good application prospects are realized.
Description
Technical field
The invention belongs to concrete admixture field, in particular to a kind of synthetic method of unsaturated Soxylat A 25-7 derivative, and the unsaturated Soxylat A 25-7 derivative adopting this synthetic method obtained, described unsaturated Soxylat A 25-7 derivative can be used for synthesizing a kind of Early-strength polycarboxylate superplasticizer.
Background technology
Polycarboxylate water-reducer is researched and developed early than the eighties in 20th century by Japanese catalyst company and is applied for a patent, belong to third generation water reducer, its water-reducing rate and function of slump protection are obviously better than conventional wooden sulfonate water reducer (first-generation water reducer) and naphthalene water reducer (s-generation water reducer), and polycarboxylate water-reducer principal reaction raw material is have the unsaturated carboxylic acid of copolyreaction activity and have the unsaturated chain shaped polymer of copolyreaction activity.
Early stage unsaturated chain shaped polymer is prepared from mainly through unsaturated carboxylic acid and polyoxyethylene glycol generation esterification, and there is no " the special polyethers of polycarboxylate water-reducer " concept in early days, polyethylene glycol compound used is field of printing and dyeing auxiliary chemicals.Early stage polycarboxylate water-reducer is ester class water reducer, reaction needed is through two steps, stability for products production efficiency and performance has a significant effect, and polyoxyethylene glycol comprises 2 terminal hydroxy group, all can with unsaturated carboxylic acid generation esterification, cause being formed the molecular structure with 2 unsaturated double-bonds, when free radicals copolymerization reaction, polymerization forms crosslinking structure, affects such polycarboxylate water-reducer dispersed.Single dibasic acid esters character is comparatively close, and by physical method for separation difficulty and cost is higher, therefore it uses and development is subject to a definite limitation.
Along with the progressively development of polycarboxylate water-reducer, for the requirement and application prospect with unsaturated chain shaped polymer, intend the chain polymer structure that research and development synthesis only has a terminal hydroxy group, this base polymer is end group reactant usually with ethylene glycol monomethyl ether, with oxyethane (EO) or propylene oxide (PO), ring-opening polymerization occurs under acid or alkaline conditions and forms.Weight-average molecular weight be 800 ~ 3000 this base polymer be considered to the earliest " the special Soxylat A 25-7 of polycarboxylate water-reducer (abbreviation modified polyether) " monomer.This base polymer effectively avoids the generation of both-end thiazolinyl molecule, improves the stability of product, but still needs, through esterification preparation, cannot realize one-step synthesis method polycarboxylate water-reducer.
After 2005, along with industry development and technical progress, first overseas enterprise synthesizes the polyoxyethylene ether derivant with copolyreaction activity double key, domestic enterprise in 2008 its also progressively realize the production of such unsaturated Soxylat A 25-7 derivative.Such polyoxyethylene ether derivant is enols used with small molecules is end group reactant, reacts in the basic conditions form with oxyethane or propylene oxide generation anionic ring-opening polymerization.Such monomer structure achieves the possibility of one-step synthesis method polycarboxylate water-reducer, the end thiazolinyl of unsaturated Soxylat A 25-7 derivative can directly and unsaturated carboxylic acid and other unsaturated compounds with copolyreaction activity synthesize polycarboxylate water-reducer by free radicals copolymerization reaction.
At present, unsaturated Soxylat A 25-7 and derivative thereof replace the chain polymer monomer needing esterification substantially, main products comprises methyl allyl alcohol polyoxyethylene ether (VPEG), allyl polyethenoxy ether (APEG), methacrylic Soxylat A 25-7 (HPEG) and isopentene group Soxylat A 25-7 (TPEG), the monomer reaction of the unsaturated Soxylat A 25-7 of different sorts and derivative thereof is active different, and reaction conditions and the performance of synthesized polycarboxylate water-reducer also have larger difference.
Soxylat A 25-7 and derivative thereof are chain-like structure, reach by sterically hindered effect mutual between Soxylat A 25-7 and derivative thereof the effect that gelling material particles is disperseed in concrete system, thus extend presetting period and final setting time, reach slow setting and protect the effect of collapsing.Tradition naphthalene water reducer is mainly through electrostatic repulsion onset of action, and in polycarboxylate water-reducer molecular structure, except playing adsorbing carboxyl and sulfonic group, polar group is less, therefore electrostatic repulsion is very little, cannot play substantial dissemination, therefore the initial water-reducing rate of polycarboxylate water-reducer and the further lifting of dispersiveness run into bottleneck.In addition, due to existing unsaturated polyoxy vinyl ether, this is slow setting functional group, for the zooming engineering of needs concrete strength, usually can only realize by adding accelerating component, and Early-strength polycarboxylate superplasticizer mostly also is the unsaturated functional group introduced and have early epistasis energy wherein, therefore, the slower development of Early-strength polycarboxylate superplasticizer.
Summary of the invention
For the shortcomings and deficiencies existed in above-mentioned prior art, in conjunction with above-mentioned reason, applicant selects the alkenyl benzene phenolic compound with unsaturated double-bond to be end group reactant, the enols used limitednumber of existing small-molecular-weight, and is difficult to introduce functional structure of functional groups further.Compound containing phenyl ring centered by phenyl ring, can connect multiple functional group, and end group reactant building form is various, is conducive in Soxylat A 25-7, introducing functional structure of functional groups by molecular designing.
Therefore, a first aspect of the present invention, provides a kind of synthetic method of unsaturated Soxylat A 25-7 derivative, comprises the following steps:
(1) with alkenyl benzene phenolic compound for starting raw material, described alkenyl benzene phenolic compound is placed in reaction vessel, rapid stirring, slowly pass into halogen gas, under UV-irradiation condition, reaction 30min ~ 60min, completes halogen substiuted reaction, obtained haloalkenyl group phenol compound A; Thus under controlling higher in temperature, that humidity is lower condition, there is halogen substiuted reaction instead of addition reaction, achieve and introduce haloid element in the molecular structure and do not destroy double bond structure;
Wherein, described alkenyl benzene phenolic compound has as the structure shown in general formula (I)-(III) any one:
Wherein, M
1for normal olefine base, M
2be hydrogen atom, methyl, ethyl, methoxyl group, oxyethyl group independently of one another.
(2) in the obtained described haloalkenyl group phenol compound A of step (1), add the alcohol compound as catalyzer, slowly pass into ammonia, and stirring reaction 60min ~ 120min; After completion of the reaction, Glacial acetic acid adjust ph is added to neutral, obtained amino substituted alkenyl phenol compound B;
(3) described amino substituted alkenyl phenol compound B step (2) obtained is as end group reactant, be placed in compressive reaction device, and add anionic ring-opening polymerization catalysts and oxyethane (EO) or propylene oxide (PO), at 150 DEG C ~ 180 DEG C and under the reaction pressure of 2.5 times of-3.5 times of standard atmospheric pressures, stirring reaction 3h ~ 8h, after anionic ring-opening polymerization reacts completely, cool the temperature to less than 55 DEG C, add Glacial acetic acid adjust ph to 6.5 ~ 7.5 again, obtained described unsaturated Soxylat A 25-7 derivative.In this step reaction, the additional proportion of different rings oxidative ethane or propylene oxide will cause the difference of the weight-average molecular weight of synthesized unsaturated Soxylat A 25-7 derivative, and corresponding reaction times and anionic ring-opening polymerization catalysts consumption also exist corresponding difference.
Preferably, described halogen gas is chlorine or bromine vapor or iodine vapor.
Preferably, described alkenyl benzene phenolic compound be selected from following any one: 2-allyl group-6-methylphenol, 4-allyl group-2,6-syringol, trans-2-oxyethyl group-5-(1-propenyl) phenol, 2-allyl group-6-methylphenol.
Preferably, described normal olefine base be following any one: vinyl, propenyl, 1-butylene base, crotyl.
Preferably, described alcohol compound be following any one: methyl alcohol, ethanol or propyl alcohol.
Preferably, described anionic ring-opening polymerization catalysts be selected from following any one: sodium methylate, potassium methylate, sodium ethylate, potassium ethylate.
According to above-mentioned synthetic method, enumerate a preferred compound 2-allyl group-6-methylphenol based on general formula (I) at this, the building-up process overview being starting raw material with it:
2-allyl group-6-methylphenol
According to above-mentioned steps (1), by itself and halogen gas under UV-irradiation condition, complete halogen substiuted reaction, obtain the intermediate a of following structure:
Intermediate a
X wherein represents Cl, Br or I.Then, according to above-mentioned steps (2), by this intermediate a under the catalysis of alcohol compound, with ammonia generation substitution reaction, generate intermediate b and ammonium chloride, described intermediate b has following structural formula:
Intermediate b
Finally, operate according to above-mentioned steps (3), by this intermediate b and oxyethane under pressurized, heated reaction conditions, by the catalysis of anionic ring-opening polymerization catalysts, complete anionic ring-opening polymerization reaction, thus obtain the target product with amido and phenyl, it is a kind of unsaturated Soxylat A 25-7 derivative, and structural formula is as follows:
N is wherein polymerization degree coefficient, and the numerical range of n should be 20 ~ 65.
Visible, a second aspect of the present invention, provide a kind of unsaturated Soxylat A 25-7 derivative obtained according to above-mentioned synthetic method, this unsaturated Soxylat A 25-7 derivative not only has C=C double bond, and has amido and phenyl.When the unsaturated Soxylat A 25-7 derivative of this synthesis is for the preparation of polycarboxylate water-reducer, the effect promoting that concrete gel material intensity rises will be had.
A third aspect of the present invention, provide a kind of preparation method of Early-strength polycarboxylate superplasticizer, it is characterized in that, above-mentioned unsaturated Soxylat A 25-7 derivative is used to be a kind of reaction raw materials, with unsaturated carboxylic acid, and other unsaturated compound with copolyreaction activity carries out free radicals copolymerization reaction, synthesizes described Early-strength polycarboxylate superplasticizer.
In addition, a fourth aspect of the present invention, provides a kind of Early-strength polycarboxylate superplasticizer using above-mentioned preparation method to synthesize.
The amidine functional group of described unsaturated Soxylat A 25-7 derivative can promote that in cement minerals component, tricalcium aluminate and tetracalcium aluminoferrite aquation form the process of ettringite structure, the formation of ettringite structure is concrete getting up early fluencing factors, therefore amino structure has the effect promoting that concrete strength rises, in concrete construction engineering, be generally suitable for the organic compound containing amido such as triethylamine, trolamine, diethanolamine as hardening accelerator.In addition, because synthesized unsaturated Soxylat A 25-7 derivative contains amido and benzene ring structure, its polarity changes, the introducing being worth amido improves the charge density of unsaturated Soxylat A 25-7 derivant structure, thus make the Soxylat A 25-7 side chain of the polycarboxylate water-reducer with its synthesis have electrostatic repulsion effect to a certain extent, be conducive to the dispersity improving cement granules in concrete, thus improve initial water-reducing rate and improve mix state.
Compared with the common polycarboxylate water-reducer synthesized under same reaction conditions, in initial water-reducing rate, cement paste divergence and intensity rising, all there is significant advantage with the polycarboxylate water-reducer that unsaturated Soxylat A 25-7 derivative of the present invention is prepared for raw material, show that the performance of unsaturated Soxylat A 25-7 derivative of the present invention is better than common unsaturated Soxylat A 25-7 of the prior art and derivative thereof, especially there is the performance that excellent promotion intensity rises, i.e. early epistasis energy.
Embodiment
Below in conjunction with embodiment, the present invention is further elaborated, but the present invention is not limited to following embodiment.
First aspect, provide a kind of synthetic method of unsaturated Soxylat A 25-7 derivative, comprise the following steps: (1) with alkenyl benzene phenolic compound for starting raw material, described alkenyl benzene phenolic compound is placed in reaction vessel, rapid stirring, slowly passes into halogen gas, under UV-irradiation condition, reaction 30min ~ 60min, completes halogen substiuted reaction, obtained haloalkenyl group phenol compound A;
Wherein, described alkenyl benzene phenolic compound has as the structure shown in general formula (I)-(III) any one:
Wherein, M
1for normal olefine base, M
2be hydrogen atom, methyl, ethyl, methoxyl group, oxyethyl group independently of one another.
(2) in the obtained described haloalkenyl group phenol compound A of step (1), add the alcohol compound as catalyzer, slowly pass into ammonia, and stirring reaction 60min ~ 120min; After completion of the reaction, Glacial acetic acid adjust ph is added to neutral, obtained amino substituted alkenyl phenol compound B;
(3) described amino substituted alkenyl phenol compound B step (2) obtained is as end group reactant, be placed in compressive reaction device, and add anionic ring-opening polymerization catalysts and oxyethane (EO) or propylene oxide (PO), at 150 DEG C ~ 180 DEG C and under the reaction pressure of 2.5 times of-3.5 times of standard atmospheric pressures, stirring reaction 3h ~ 8h, after anionic ring-opening polymerization reacts completely, cool the temperature to less than 55 DEG C, add Glacial acetic acid adjust ph to 6.5 ~ 7.5 again, obtained described unsaturated Soxylat A 25-7 derivative.
In a preferred embodiment, described halogen gas is chlorine or bromine vapor or iodine vapor.
In a preferred embodiment, described alkenyl benzene phenolic compound be selected from following any one: 2-allyl group-6-methylphenol, 4-allyl group-2,6-syringol, trans-2-oxyethyl group-5-(1-propenyl) phenol, 2-allyl group-6-methylphenol.
In a preferred embodiment, described normal olefine base be following any one: vinyl, propenyl, 1-butylene base, crotyl.
In a preferred embodiment, described alcohol compound be following any one: methyl alcohol, ethanol or propyl alcohol.
In a preferred embodiment, described anionic ring-opening polymerization catalysts be selected from following any one: sodium methylate, potassium methylate, sodium ethylate, potassium ethylate.
Second aspect, provides a kind of unsaturated Soxylat A 25-7 derivative obtained according to above-mentioned synthetic method.
The third aspect, provide a kind of preparation method of Early-strength polycarboxylate superplasticizer, it is characterized in that, above-mentioned unsaturated Soxylat A 25-7 derivative is used to be a kind of reaction raw materials, with unsaturated carboxylic acid, and other unsaturated compound with copolyreaction activity carries out free radicals copolymerization reaction, synthesizes described Early-strength polycarboxylate superplasticizer.
Fourth aspect, provides a kind of Early-strength polycarboxylate superplasticizer using above-mentioned preparation method to synthesize.
Step in the preparation method of following unsaturated Soxylat A 25-7 derivative is ordinary method if no special instructions, and described starting material all can obtain from open commercial sources if no special instructions.
Embodiment 1
500g2-allyl group-6-methylphenol is added in flask, rapid stirring, and slowly pass into chlorine, in UV-light reaction box, react 45min, be i.e. obtained 2-allyl group-6-chloro-methyl phenol.Add ethanol in proper amount as catalyzer, slowly pass into ammonia, stirring reaction 90min, add Glacial acetic acid and regulate pH value to neutral, obtain 2-allyl group-6-amine methylphenol.
It is in the compressive reaction device of 5L that the 2-allyl group-6-amine methylphenol prepared by 150g adds volume, add 50g sodium methylate as catalyzer, add 2000g oxyethane (EO), stirring reaction to control temperature of reaction be 165 DEG C, reaction unit internal pressure is 3.0 times of standard atmospheric pressures, and the reaction times is 5h.After reaction terminates, cool the temperature to 50 DEG C, add appropriate Glacial acetic acid and regulate pH value to 7.5, namely obtain the unsaturated Soxylat A 25-7 derivative containing amido and benzene ring structure that weight-average molecular weight is about 2200.
Embodiment 2
500g4-allyl group-2,6-syringol is added in flask, rapid stirring, and slowly pass into chlorine, in UV-light reaction box, react 60min, be i.e. obtained 4-allyl group-2,6-dichloro methoxyphenol.Add ethanol in proper amount as catalyzer, slowly pass into ammonia, stirring reaction 120min, add Glacial acetic acid and regulate pH value to neutral, obtain 4-allyl group-2,6-diamines methoxyphenol.
4-allyl group-2 prepared by 200g, it is in the compressive reaction device of 5L that 6-diamines methoxyphenol adds volume, add 60g sodium ethylate as catalyzer, add 2000g oxyethane (EO), stirring reaction to control temperature of reaction be 180 DEG C, reaction unit internal pressure is 3.5 times of standard atmospheric pressures, and the reaction times is 4.5h.After reaction terminates, cool the temperature to 50 DEG C, add appropriate Glacial acetic acid and regulate pH value to 7.5, namely obtain weight-average molecular weight and be about the unsaturated Soxylat A 25-7 derivative that 2200 contain amido and benzene ring structure.
Embodiment 3
Trans for 500g-2-oxyethyl group-5-(1-propenyl) phenol is added in flask, rapid stirring, and slowly pass into bromine vapor, in UV-light reaction box, react 30min, be i.e. obtained trans-2-bromine oxethyl-5-(1-propenyl) phenol.Add appropriate propyl alcohol as catalyzer, slowly pass into ammonia, stirring reaction 120min, add Glacial acetic acid and regulate pH value to neutral, be trans-2-aminoethoxy-5-(1-propenyl) phenol.
It is in the compressive reaction device of 5L that trans-2-aminoethoxy-5-(1-propenyl) phenol prepared by 160g adds volume, add 60g potassium ethylate as catalyzer, add 2000g propylene oxide (PO), stirring reaction to control temperature of reaction be 180 DEG C, reaction unit internal pressure is 3.5 times of standard atmospheric pressures, and the reaction times is 6.5h.After reaction terminates, cool the temperature to 50 DEG C, add appropriate Glacial acetic acid and regulate pH value to 7.5, obtain weight-average molecular weight and be about the unsaturated Soxylat A 25-7 derivative that 2200 contain amido and benzene ring structure.
Embodiment 4
500g2-allyl group-6-methylphenol is added in flask, rapid stirring, and slowly pass into iodine vapor, in UV-light reaction box, react 45min, obtain 2-allyl group-6-iodomethyl phenol.Add proper amount of methanol as catalyzer, slowly pass into ammonia, stirring reaction 60min, add Glacial acetic acid and regulate pH value to neutral, be i.e. obtained 2-allyl group-6-amine methylphenol.
It is in the compressive reaction device of 5L that the 2-allyl group-6-amine methylphenol prepared by 150g adds volume, add 50g sodium methylate as catalyzer, add 1000g oxyethane (EO), stirring reaction to control temperature of reaction be 150 DEG C, reaction unit internal pressure is 2.5 times of standard atmospheric pressures, and the reaction times is 3.5h.After reaction terminates, cool the temperature to 50 DEG C, add appropriate Glacial acetic acid and regulate pH value to 7.5, namely obtained weight-average molecular weight is about the unsaturated Soxylat A 25-7 derivative that 1200 contain amido and benzene ring structure.
Embodiment 5
500g2-allyl group-6-methylphenol is added in flask, rapid stirring, and slowly pass into chlorine, in UV-light reaction box, react 50min, obtain 2-allyl group-6-chloro-methyl phenol.Add appropriate propyl alcohol as catalyzer, slowly pass into ammonia, stirring reaction 75min, add Glacial acetic acid and regulate pH value to neutral, obtain 2-allyl group-6-amine methylphenol.
It is in the compressive reaction device of 5L that the 2-allyl group-6-amine methylphenol prepared by 75g adds volume, add 50g sodium methylate as catalyzer, add 2000g propylene oxide (EO), stirring reaction to control temperature of reaction be 175 DEG C, reaction unit internal pressure is 3.3 times of standard atmospheric pressures, and the reaction times is 7h.After reaction terminates, cool the temperature to 50 DEG C, add appropriate Glacial acetic acid and regulate pH value to 7.5, obtain the unsaturated Soxylat A 25-7 derivative containing amido and benzene ring structure that weight-average molecular weight is about 3500.
Below, respectively with according to the unsaturated Soxylat A 25-7 derivative containing amido and benzene ring structure of the method for the invention synthesis, methacrylic Soxylat A 25-7 (HPEG) and isopentene group Soxylat A 25-7 (TPEG) for reaction raw materials, polycarboxylate water-reducer is synthesized, the mensuration of line correlation performance of going forward side by side under identical material ratio and same reaction conditions.
Testing cement used is Shanghai conch 42.5 ordinary portland cement, and test water-reducing rate and cement paste divergence with reference to GB/8076-2008, expansion diameter units is millimeter (mm), and experimental result is as following table 1:
Table 1
Shown by water-reducing rate and cement paste divergence test result, under the same terms, with the water-reducing rate of the different sorts unsaturated polyether polycarboxylate water-reducer that is Material synthesis and cement paste divergence, there is some difference: wherein TPEG is that the water-reducing rate of monomer synthesize polycarboxylate water-reducer and cement paste divergence are a little more than the polycarboxylate water-reducer taking HPEG as Material synthesis, but difference is also not obvious, and overall performance is close; And according to the unsaturated Soxylat A 25-7 derivative that the method for the invention is synthesized, containing amido and phenyl ring, revolutionize the system tension force of cement slurry, and make to have between cement granules comparatively significantly electrostatic repulsion effect, thus significantly improve water-reducing rate and cement paste divergence.
In addition, carry out the husky system Strength Changes of corresponding glue and measure, data results is as following table 2:
Table 2
The polycarboxylate water-reducer of common polyether synthesis has stronger delayed coagulation, initial strength rises comparatively slow, is difficult to reach basic mechanical strength within a short period of time, is therefore unfavorable for the application of the concrete works of needs epistasis morning energy, along with the test block maintenance time increases, intensity rises gradually; The polycarboxylate water-reducer intensity difference of the Amino-phenyl polyethers that the polycarboxylate water-reducer of common polyether synthesis and the present invention synthesize obviously reduces.This shows that the introducing of amido promotes that premature gelation material mineral constituent aquation forms the process of ettringite structure, tricalcium aluminate and tetracalcium aluminoferrite reacted after, intensity rises and mainly relies on the heat evolution velocity of Dicalcium Phosphate (Feed Grade) and tricalcium silicate, amido is little on its impact, therefore the monomer that the present invention synthesizes within the initial short period is conducive to intensity and rises fast, is adapted to the application of the early strong concrete works required.
Be described in detail specific embodiments of the invention above, but it is just as example, the present invention is not restricted to specific embodiment described above.To those skilled in the art, any equivalent modifications that the present invention is carried out and substituting also all among category of the present invention.Therefore, equalization conversion done without departing from the spirit and scope of the invention and amendment, all should contain within the scope of the invention.
Claims (9)
1. a synthetic method for unsaturated Soxylat A 25-7 derivative, comprises the following steps:
(1) with alkenyl benzene phenolic compound for starting raw material, described alkenyl benzene phenolic compound is placed in reaction vessel, rapid stirring, slowly pass into halogen gas, under UV-irradiation condition, reaction 30min ~ 60min, completes halogen substiuted reaction, obtained haloalkenyl group phenol compound A; Wherein, described alkenyl benzene phenolic compound has as the structure shown in general formula (I)-(III) any one:
Wherein, M
1for normal olefine base, M
2be hydrogen atom, methyl, ethyl, methoxyl group, oxyethyl group independently of one another;
(2) in the obtained described haloalkenyl group phenol compound A of step (1), add the alcohol compound as catalyzer, slowly pass into ammonia, and stirring reaction 60min ~ 120min; After completion of the reaction, Glacial acetic acid adjust ph is added to neutral, obtained amino substituted alkenyl phenol compound B;
(3) described amino substituted alkenyl phenol compound B step (2) obtained is as end group reactant, be placed in compressive reaction device, and add anionic ring-opening polymerization catalysts and oxyethane (EO) or propylene oxide (PO), at 150 DEG C ~ 180 DEG C and under the reaction pressure of 2.5 times of-3.5 times of standard atmospheric pressures, stirring reaction 3h ~ 8h, after anionic ring-opening polymerization reacts completely, cool the temperature to less than 55 DEG C, add Glacial acetic acid adjust ph to 6.5 ~ 7.5 again, obtained described unsaturated Soxylat A 25-7 derivative.
2. the synthetic method of unsaturated Soxylat A 25-7 derivative according to claim 1, is characterized in that, described halogen gas is chlorine or bromine vapor or iodine vapor.
3. the synthetic method of unsaturated Soxylat A 25-7 derivative according to claim 1, it is characterized in that, described alkenyl benzene phenolic compound be selected from following any one: 2-allyl group-6-methylphenol, 4-allyl group-2,6-syringol, trans-2-oxyethyl group-5-(1-propenyl) phenol, 2-allyl group-6-methylphenol.
4. the synthetic method of unsaturated Soxylat A 25-7 derivative according to claim 1, is characterized in that, described normal olefine base be following any one: vinyl, propenyl, 1-butylene base, crotyl.
5. the synthetic method of unsaturated Soxylat A 25-7 derivative according to claim 1, is characterized in that, described alcohol compound be following any one: methyl alcohol, ethanol or propyl alcohol.
6. the synthetic method of unsaturated Soxylat A 25-7 derivative according to claim 1, is characterized in that, described anionic ring-opening polymerization catalysts be selected from following any one: sodium methylate, potassium methylate, sodium ethylate, potassium ethylate.
7. the unsaturated Soxylat A 25-7 derivative that the synthetic method according to above-mentioned any one claim is obtained.
8. the preparation method of an Early-strength polycarboxylate superplasticizer, it is characterized in that, unsaturated Soxylat A 25-7 derivative as claimed in claim 7 is used to be a kind of reaction raw materials, with unsaturated carboxylic acid, and other unsaturated compound with copolyreaction activity carries out free radicals copolymerization reaction, synthesizes described Early-strength polycarboxylate superplasticizer.
9. one kind adopts the Early-strength polycarboxylate superplasticizer of preparation method as claimed in claim 8 synthesis.
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| CN112812289A (en) * | 2021-01-21 | 2021-05-18 | 吉林瑞吉特殊化学品有限公司 | Anti-mud ethoxylated naphthalene aromatic ring derivative monomer and preparation method thereof |
| CN112961289A (en) * | 2021-02-09 | 2021-06-15 | 武汉理工大学 | High-durability water reducing agent and preparation method thereof |
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| JP2014208763A (en) * | 2013-03-29 | 2014-11-06 | 荒川化学工業株式会社 | Water-soluble polymer pigment dispersant and aqueous composition containing the same |
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| CN103011669A (en) * | 2012-12-20 | 2013-04-03 | 南京瑞迪高新技术有限公司 | Early-strength polycarboxylate superplasticizer and preparation method thereof |
| CN103145364A (en) * | 2013-03-18 | 2013-06-12 | 珠海聚特科技有限公司 | Sulfoacid modified polycarboxylic superplasticizer and preparation method thereof |
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| CN112812289A (en) * | 2021-01-21 | 2021-05-18 | 吉林瑞吉特殊化学品有限公司 | Anti-mud ethoxylated naphthalene aromatic ring derivative monomer and preparation method thereof |
| CN112961289A (en) * | 2021-02-09 | 2021-06-15 | 武汉理工大学 | High-durability water reducing agent and preparation method thereof |
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