CN105273180B - A kind of synthetic method of unsaturated polyoxyethylene ether derivant and products thereof - Google Patents
A kind of synthetic method of unsaturated polyoxyethylene ether derivant and products thereof Download PDFInfo
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Abstract
The invention provides a kind of synthetic method of unsaturated polyoxyethylene ether derivant, i.e. using alkenyl phenol compound as initiation material, halogen substitution reaction is carried out with halogen gas, with ammonia substitution reaction occurs for gained haloalkenyl group phenol compound A again, generate amino substituted alkenyl phenol compound B, polymerisation finally is completed with oxirane (EO) or expoxy propane (PO), target product is made.Present invention also offers a kind of unsaturated polyoxyethylene ether derivant prepared using the above method, the unsaturated polyoxyethylene ether derivant can be used for the preparation of polycarboxylate water-reducer, so that the polycarboxylate water-reducer has excellent early strong effect, there is good application prospect.
Description
Technical field
The invention belongs to the additive field of concrete, more particularly to a kind of synthesis of unsaturated polyoxyethylene ether derivant
Method, and derived using unsaturated polyoxyethylene ether derivant made from the synthetic method, the unsaturated APEO
Thing can be used for synthesizing a kind of Early-strength polycarboxylate superplasticizer.
Background technology
Polycarboxylate water-reducer is most researched and developed and applied for a patent by Japanese catalyst company earlier than the 1980s, belongs to the third generation
Water reducer, its water-reducing rate and function of slump protection are substantially better than conventional wooden sulfonate water reducer (first generation water reducer) and naphthalene system diminishing
Agent (second generation water reducer), polycarboxylate water-reducer key reaction raw material be with copolyreaction activity unsaturated carboxylic acid with
The unsaturated chain shaped polymer of copolyreaction activity.
The unsaturated chain shaped polymer of early stage mainly by unsaturated carboxylic acid and polyethylene glycol occur esterification prepare and
Into having no " the special polyethers of polycarboxylate water-reducer " concept in early days, polyethylene glycol compound used is field of printing and dyeing auxiliary chemicals.It is early
Phase polycarboxylate water-reducer is esters water reducer, and reaction is needed by two steps, for the steady of production efficiency and performance
It is qualitative to have a significant effect, and polyethylene glycol includes 2 terminal hydroxy groups, esterification can occur with unsaturated carboxylic acid, cause shape
Into the molecular structure with 2 unsaturated double-bonds, it polymerize to form cross-linked structure in free radicals copolymerization reaction, influences the carboxylic of birdsing of the same feather flock together
Sour water reducer dispersiveness.Single dibasic acid esters property is closer to, and cost difficult by physical method for separation is higher, thus its using and
Development is by a definite limitation.
With the progressively development of polycarboxylate water-reducer, for the demand and application prospect with unsaturated chain shaped polymer, intend
Research and development synthesis only has the chain polymer structure of a terminal hydroxy group, and such polymer generally reacts by end group of glycol monoethyl ether
Thing, ring-opening polymerization occurs with oxirane (EO) or expoxy propane (PO) under acid or alkaline conditions and forms.Divide equally again
Son amount is considered as that earliest " the special APEO of polycarboxylate water-reducer is (referred to as modified for 800~3000 such polymer
Polyethers) " monomer.Such polymer effectively avoids the generation of both-end alkenyl molecule, improves the stability of product, but still needs
Prepared by esterification, one-step synthesis method polycarboxylate water-reducer can not be realized.
After 2005, with industry development and technological progress, overseas enterprise synthesizes with copolyreaction activity double key first
Polyoxyethylene ether derivant, domestic enterprise in 2008 its life of such unsaturated polyoxyethylene ether derivant is also done step-by-step
Production.Such polyoxyethylene ether derivant is enols used for end group reactant with small molecule, in the basic conditions with epoxy second
Alkane or expoxy propane occur anionic ring-opening polymerization reaction and formed.Such monomer structure realizes one-step synthesis method polycarboxylic acids diminishing
The possibility of agent, the end alkenyl of unsaturated polyoxyethylene ether derivant can directly with unsaturated carboxylic acid and other there is copolyreaction
The unsaturated compound of activity synthesizes polycarboxylate water-reducer by free radicals copolymerization reaction.
At present, substitution needs the chain polymer list of esterification substantially for unsaturated APEO and its derivative
Body, major product include methyl allyl alcohol polyoxyethylene ether (VPEG), allyl polyethenoxy ether (APEG), methacrylic and gathered
Oxygen vinethene (HPEG) and isopentene group APEO (TPEG), variety classes unsaturation APEO and its derivative
Monomer reaction activity is different, and the reaction condition and performance of synthesized polycarboxylate water-reducer also have larger difference.
APEO and its derivative are chain structure, pass through APEO and its derivative in concrete system
Between mutual steric hindrance effect have the function that to make gelling material particles scattered, during so as to extend presetting period and final set
Between, reach slow setting and protect the effect collapsed.Traditional naphthalene water reducer is mainly by electrostatic repulsion onset of action, and polycarboxylate water-reducer divides
In minor structure, in addition to the carboxyl and sulfonic group for playing suction-operated, polar group is less, therefore electrostatic repulsion very little, can not play
Substantial peptizaiton, therefore the further lifting of the initial water-reducing rate of polycarboxylate water-reducer and dispersiveness runs into bottleneck.This
Outside, because existing unsaturated APEO is essentially slow setting functional group, for needing the zooming engineering of concrete strength,
It is typically only possible by adding accelerating component realization, and Early-strength polycarboxylate superplasticizer is also mostly to introduce to have early epistasis energy wherein
Unsaturated functional group, therefore, the slower development of Early-strength polycarboxylate superplasticizer.
The content of the invention
For shortcomings and deficiencies present in above-mentioned prior art, with reference to above-mentioned reason, applicant, which selects, has unsaturation
The alkenyl phenol compound of double bond is end group reactant, the existing enols used limitednumber of small-molecular-weight, and is difficult to
It is further introduced into feature structure of functional groups.Compound containing phenyl ring can connect multiple functional groups centered on phenyl ring, end
Base reactant building form is various, is advantageous to introduce feature structure of functional groups in APEO by MOLECULE DESIGN.
Therefore, the first aspect of the present invention, there is provided a kind of synthetic method of unsaturated polyoxyethylene ether derivant, including
Following steps：
(1) using alkenyl phenol compound as initiation material, the alkenyl phenol compound is placed in reaction vessel,
Quick stirring, is slowly introducing halogen gas, under the conditions of ultraviolet light, reacts 30min~60min, and it is anti-to complete halogen substitution
Should, haloalkenyl group phenol compound A is made；So as to control under conditions of temperature is higher, humidity is relatively low, halogen substitution occurs
Reaction rather than addition reaction, realize introducing halogen in the molecular structure and do not destroy double bond structure；
Wherein, the alkenyl phenol compound has as led to the structure shown in any of formula (I)-(III)：
Wherein, M1For linear alkene base, M2It is each independently hydrogen atom, methyl, ethyl, methoxyl group, ethyoxyl.
(2) toward alcohols chemical combination of the addition as catalyst in the haloalkenyl group phenol compound A made from step (1)
Thing, it is slowly introducing ammonia, and stirring reaction 60min~120min；After completion of the reaction, add glacial acetic acid and adjust pH value to neutrality,
Amino substituted alkenyl phenol compound B is made；
(3) using the amino substituted alkenyl phenol compound B made from step (2) as end group reactant, it is placed in and adds
Press in reaction unit, and add anionic ring-opening polymerization catalysts and oxirane (EO) or expoxy propane (PO), 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, anionic ring-opening polymerization
After reaction completely, less than 55 DEG C are cooled the temperature to, glacial acetic acid is added and adjusts pH value to 6.5~7.5, be made described unsaturated poly-
Oxygen ethene ether derivant.At this in step reaction, the additional proportions of different oxirane or expoxy propane will cause it is synthesized not
The difference of the weight average molecular weight of saturation polyoxyethylene ether derivant, corresponding reaction time and anionic ring-opening polymerization catalytic reaction
There is also corresponding difference for agent dosage.
Preferably, the halogen gas is chlorine or bromine vapor or iodine vapor.
Preferably, the alkenyl phenol compound is selected from following any：2- pi-allyl -6- methylphenols, 4- allyls
Base -2,6- syringol, trans -2- ethyoxyls -5- (1- acrylic) phenol, 2- pi-allyl -6- methylphenols.
Preferably, the linear alkene base is following any：Vinyl, acrylic, 1- cyclobutenyls, 2- cyclobutenyls.
Preferably, the alcohol compound is following any：Methanol, ethanol or propyl alcohol.
Preferably, the anionic ring-opening polymerization catalysts are selected from following any：Sodium methoxide, potassium methoxide, ethanol
Sodium, potassium ethoxide.
According to above-mentioned synthetic method, a preferred compound 2- pi-allyl -6- first based on leading to formula (I) is enumerated herein
Base phenol, the building-up process overview using it as initiation material：
2- pi-allyl -6- methylphenols
According to above-mentioned steps (1), by its with halogen gas under the conditions of ultraviolet light, complete halogen substitution reaction, obtain
To the intermediate a of following structure：
Intermediate a
X therein represents Cl, Br or I.Then, according to above-mentioned steps (2), by intermediate a urging in alcohol compound
Under change, substitution reaction occurs with ammonia, generating intermediate b and ammonium chloride, the intermediate b has following structural formula：
Intermediate b
Finally, operated according to above-mentioned steps (3), by intermediate b and oxirane under pressurized, heated reaction condition, quilt
Anionic ring-opening polymerization catalysts are catalyzed, and complete anionic ring-opening polymerization reaction, so as to obtain having amido and phenyl
Target product, it is a kind of unsaturated polyoxyethylene ether derivant, and structural formula is as follows：
N therein is degree of polymerization coefficient, and n number range should be 20~65.
A kind of it can be seen that the second aspect of the present invention, there is provided polyoxyethylene unsaturated according to made from above-mentioned synthetic method
Ether derivant, the unsaturated polyoxyethylene ether derivant not only has C=C double bonds, and has amido and phenyl.When the synthesis
Unsaturated polyoxyethylene ether derivant be used for when preparing polycarboxylate water-reducer, will have and promote in concrete gel material intensity
The effect risen.
A kind of the third aspect of the present invention, there is provided preparation method of Early-strength polycarboxylate superplasticizer, it is characterised in that make
It is a kind of reaction raw materials with above-mentioned unsaturated polyoxyethylene ether derivant, and unsaturated carboxylic acid, and other there is copolyreaction
The unsaturated compound of activity carries out free radicals copolymerization reaction, synthesizes the Early-strength polycarboxylate superplasticizer.
In addition, the fourth aspect of the present invention, there is provided a kind of early-strength polycarboxylic acids synthesized using above-mentioned preparation method is subtracted
Aqua.
The amidine functional group of the unsaturated polyoxyethylene ether derivant can promote tricalcium aluminate in cement minerals component
The process of ettringite structure is formed with tetra calcium aluminoferrite aquation, the formation of entringite structure is the master that concrete getting up early influences intensity
Factor is wanted, therefore amino structure plays the role of to promote concrete strength to rise, and in concrete construction engineering, is generally applicable three second
Amine, triethanolamine, diethanol amine etc. contain the organic compound of amido as early strength agent.It is further, since synthesized unsaturated poly-
Oxygen ethene ether derivant contains amido and benzene ring structure, and its polarity changes, and the introducing for being worth amido improves unsaturated gather
The charge density of oxygen vinethene derivant structure, so as to cause the polyoxy of the polycarboxylate water-reducer with its synthesis to a certain extent
Vinethene side chain has electrostatic repulsion effect, is advantageous to improve the decentralization of cement granules in concrete, initially subtracts so as to improve
Water rate and improvement mix state.
Compared with the common polycarboxylate water-reducer synthesized under same reaction conditions, with unsaturated polyoxy second of the present invention
Alkene ether derivant is that polycarboxylate water-reducer prepared by raw material is equal in terms of initial water-reducing rate, cement paste divergence and intensity rising
With significant advantage, show that the performance of unsaturated polyoxyethylene ether derivant of the present invention is common better than of the prior art
Unsaturated APEO and its derivative, the performance especially risen with excellent promotion intensity, i.e., early epistasis energy.
Embodiment
With reference to embodiment, the present invention is further elaborated, but the present invention is not limited to following embodiment party
Formula.
First aspect, there is provided a kind of synthetic method of unsaturated polyoxyethylene ether derivant, comprise the following steps：(1)
Using alkenyl phenol compound as initiation material, the alkenyl phenol compound is placed in reaction vessel, quick stirring, delayed
Slowly halogen gas is passed through, under the conditions of ultraviolet light, reacts 30min~60min, complete halogen substitution reaction, halo is made
Alkenyl phenol compound A；
Wherein, the alkenyl phenol compound has as led to the structure shown in any of formula (I)-(III)：
Wherein, M1For linear alkene base, M2It is each independently hydrogen atom, methyl, ethyl, methoxyl group, ethyoxyl.
(2) toward alcohols chemical combination of the addition as catalyst in the haloalkenyl group phenol compound A made from step (1)
Thing, it is slowly introducing ammonia, and stirring reaction 60min~120min；After completion of the reaction, add glacial acetic acid and adjust pH value to neutrality,
Amino substituted alkenyl phenol compound B is made；
(3) using the amino substituted alkenyl phenol compound B made from step (2) as end group reactant, it is placed in and adds
Press in reaction unit, and add anionic ring-opening polymerization catalysts and oxirane (EO) or expoxy propane (PO), 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, anionic ring-opening polymerization
After reaction completely, less than 55 DEG C are cooled the temperature to, glacial acetic acid is added and adjusts pH value to 6.5~7.5, be made described unsaturated poly-
Oxygen ethene ether derivant.
In a preferred embodiment, the halogen gas is chlorine or bromine vapor or iodine vapor.
In a preferred embodiment, the alkenyl phenol compound is selected from following any：2- pi-allyl -6- methyl
Phenol, 4- pi-allyls -2,6- syringol, trans -2- ethyoxyls -5- (1- acrylic) phenol, 2- pi-allyl -6- methyl
Phenol.
In a preferred embodiment, the linear alkene base is following any：Vinyl, acrylic, 1- cyclobutenyls,
2- cyclobutenyls.
In a preferred embodiment, the alcohol compound is following any：Methanol, ethanol or propyl alcohol.
In a preferred embodiment, the anionic ring-opening polymerization catalysts are selected from following any：Sodium methoxide,
Potassium methoxide, caustic alcohol, potassium ethoxide.
A kind of second aspect, there is provided polyoxyethylene ether derivant unsaturated according to made from above-mentioned synthetic method.
The third aspect, there is provided a kind of preparation method of Early-strength polycarboxylate superplasticizer, it is characterised in that use is above-mentioned not
Saturation polyoxyethylene ether derivant is a kind of reaction raw materials, and unsaturated carboxylic acid, and other has copolyreaction activity not
Saturated compounds carries out free radicals copolymerization reaction, synthesizes the Early-strength polycarboxylate superplasticizer.
A kind of fourth aspect, there is provided Early-strength polycarboxylate superplasticizer synthesized using above-mentioned preparation method.
Step in the preparation method of following unsaturated polyoxyethylene ether derivants is conventional method unless otherwise instructed,
The raw material can obtain from open commercial sources unless otherwise instructed.
Embodiment 1
500g 2- pi-allyl -6- methylphenols are added in flask, quick stirring, and be slowly introducing chlorine, in ultraviolet light
45min is reacted in reaction chamber, that is, 2- pi-allyl -6- chloro-methyl phenols are made.Ethanol in proper amount is added as catalyst, is slowly introducing
Ammonia, stirring reaction 90min, add glacial acetic acid and adjust pH value to neutrality, produce 2- pi-allyl -6- amine methylphenols.
2- pi-allyl -6- amine methylphenol prepared by 150g is added in the compressive reaction device that volume is 5L, adds 50g
Sodium methoxide adds 2000g oxirane (EO), stirring reaction and controlling reaction temperature are 165 DEG C, reaction unit as catalyst
Internal pressure is 3.0 times of standard atmospheric pressures, reaction time 5h.After reaction terminates, 50 DEG C are cooled the temperature to, adds appropriate ice vinegar
Acid regulation pH value obtains the unsaturated polyoxyethylene containing amido and benzene ring structure that weight average molecular weight is about 2200 to 7.5
Ether derivant.
Embodiment 2
500g 4- pi-allyls -2,6- syringol is added in flask, quick stirring, and be slowly introducing chlorine,
60min is reacted in ultraviolet light reaction chamber, that is, 4- pi-allyl -2,6- dichloro metoxyphenols are made.Addition ethanol in proper amount, which is used as, urges
Agent, ammonia is slowly introducing, stirring reaction 120min, glacial acetic acid is added and adjusts pH value to neutrality, produce 4- pi-allyls -2,6- bis-
Amine metoxyphenol.
4- pi-allyl -2,6- diamines metoxyphenol prepared by 200g is added in the compressive reaction device that volume is 5L,
Adding 60g caustic alcohols and be used as catalyst, add 2000g oxirane (EO), stirring reaction and controlling reaction temperature are 180 DEG C,
Reaction unit internal pressure is 3.5 times of standard atmospheric pressures, reaction time 4.5h.After reaction terminates, 50 DEG C are cooled the temperature to, is added
Enter appropriate glacial acetic acid and adjust pH value to 7.5, that is, it is about 2200 unsaturations containing amido and benzene ring structure to obtain weight average molecular weight
Polyoxyethylene ether derivant.
Embodiment 3
500g trans -2- ethyoxyls -5- (1- acrylic) phenol is added in flask, quick stirring, and be slowly introducing bromine
Steam, 30min is reacted in ultraviolet light reaction chamber, that is, trans -2- bromine oxethyls -5- (1- acrylic) phenol is made.Add suitable
Propyl alcohol is measured as catalyst, ammonia is slowly introducing, stirring reaction 120min, adds glacial acetic acid and adjust pH value to neutrality, be anti-
Formula -2- aminoethoxies -5- (1- acrylic) phenol.
Trans -2- aminoethoxies -5- (1- acrylic) phenol prepared by 160g adds the compressive reaction that volume is 5L
In device, 60g potassium ethoxides are added as catalyst, add 2000g expoxy propane (PO), simultaneously controlling reaction temperature is stirring reaction
180 DEG C, reaction unit internal pressure is 3.5 times of standard atmospheric pressures, reaction time 6.5h.After reaction terminates, cool the temperature to
50 DEG C, add appropriate glacial acetic acid and adjust pH value to 7.5, produce weight average molecular weight be about 2200 containing amido and benzene ring structure not
Saturation polyoxyethylene ether derivant.
Embodiment 4
500g 2- pi-allyl -6- methylphenols are added in flask, quick stirring, and be slowly introducing iodine vapor, ultraviolet
45min is reacted in light reaction case, produces 2- pi-allyl -6- iodomethyl phenol.Proper amount of methanol is added as catalyst, is slowly introducing
Ammonia, stirring reaction 60min, add glacial acetic acid and adjust pH value to neutrality, that is, 2- pi-allyl -6- amine methylphenols are made.
2- pi-allyl -6- amine methylphenol prepared by 150g is added in the compressive reaction device that volume is 5L, adds 50g
Sodium methoxide adds 1000g oxirane (EO), stirring reaction and controlling reaction temperature are 150 DEG C, reaction unit as catalyst
Internal pressure is 2.5 times of standard atmospheric pressures, reaction time 3.5h.After reaction terminates, 50 DEG C are cooled the temperature to, adds appropriate ice
Acetic acid adjusts pH value to 7.5, that is, it is about the 1200 unsaturated polyoxyethylene containing amido and benzene ring structure that weight average molecular weight, which is made,
Ether derivant.
Embodiment 5
500g 2- pi-allyl -6- methylphenols are added in flask, quick stirring, and be slowly introducing chlorine, in ultraviolet light
50min is reacted in reaction chamber, produces 2- pi-allyl -6- chloro-methyl phenols.Appropriate propyl alcohol is added as catalyst, is slowly introducing ammonia
Gas, stirring reaction 75min, add glacial acetic acid and adjust pH value to neutrality, produce 2- pi-allyl -6- amine methylphenols.
2- pi-allyl -6- amine methylphenol prepared by 75g is added in the compressive reaction device that volume is 5L, adds 50g
Sodium methoxide adds 2000g expoxy propane (EO), stirring reaction and controlling reaction temperature are 175 DEG C, reaction unit as catalyst
Internal pressure is 3.3 times of standard atmospheric pressures, reaction time 7h.After reaction terminates, 50 DEG C are cooled the temperature to, adds appropriate ice vinegar
Acid regulation pH value produces the unsaturated APEO containing amido and benzene ring structure that weight average molecular weight is about 3500 to 7.5
Derivative.
Below, respectively with the unsaturated polyoxyethylene containing amido and benzene ring structure according to the method for the invention synthesis
Ether derivant, methyl allyl polyoxyethylene ether (HPEG) and isopentene group APEO (TPEG) are reaction raw materials, in phase
With synthesizing polycarboxylate water-reducer under material ratio and same reaction conditions, and carry out the measure of correlated performance.
Cement used in experiment is the ordinary portland cement of Shanghai conch 42.5, tests water-reducing rate with reference to GB/8076-2008 and cement is net
Divergence is starched, extension diameter units are millimeter (mm), experimental result such as table 1 below：
Table 1
Shown by water-reducing rate and cement paste divergence test result, under the same terms using variety classes unsaturated polyether as
There is some difference for the water-reducing rate and cement paste divergence of the polycarboxylate water-reducer of Material synthesis：Wherein TPEG synthesizes for monomer
The water-reducing rate and cement paste divergence of polycarboxylate water-reducer are slightly above the polycarboxylate water-reducer using HPEG as Material synthesis, but poor
Not and unobvious, overall performance approach；And according to the unsaturated polyoxyethylene ether derivant of the method for the invention synthesis, contain
Amido and phenyl ring, revolutionize the system tension force of cement slurry, and make have more obvious electrostatic repulsion between cement granules
Effect, so as to significantly improve water-reducing rate and cement paste divergence.
In addition, carry out corresponding glue sand system Strength Changes measure, data result such as table 2 below：
Table 2
The polycarboxylate water-reducer of common polyether synthesis has stronger deferred action, and initial strength rises slower, it is difficult to
Reach basic mechanical strength in short period, therefore be unfavorable for needing the application of the concrete works of early epistasis energy, with examination
Block curing time increases, and intensity is gradually increasing；The Amino-phenyl that the polycarboxylate water-reducer of common polyether synthesis synthesizes with the present invention
The polycarboxylate water-reducer intensity difference of polyethers is obviously reduced.This shows that the introducing of amido promotes premature gelation material mineral constituent water
Change the process for forming ettringite structure, after tricalcium aluminate and tetra calcium aluminoferrite react, intensity, which rises, relies primarily on dicalcium silicate
With the heat evolution velocity of tricalcium silicate, amido influences less on it, therefore the monomer that the present invention synthesizes within the initial short period has
Beneficial to intensity rapid increase, it is adapted to the application of the concrete works of early strong demand.
The specific embodiment of the present invention is described in detail above, but it is intended only as example, it is of the invention and unlimited
It is formed on particular embodiments described above.To those skilled in the art, it is any to the equivalent modifications that carry out of the present invention and
Substitute also all among scope of the invention.Therefore, the impartial conversion made without departing from the spirit and scope of the invention and
Modification, all should be contained within the scope of the invention.
Claims (9)
1. a kind of synthetic method of unsaturated polyoxyethylene ether derivant, comprises the following steps：
(1) using alkenyl phenol compound as initiation material, the alkenyl phenol compound is placed in reaction vessel, quickly
Stirring, is slowly introducing halogen gas, under the conditions of ultraviolet light, reacts 30min~60min, completes halogen substitution reaction, system
Obtain haloalkenyl group phenol compound A；Wherein, the alkenyl phenol compound has such as any of logical formula (I)-(III)
Shown structure：
Wherein, M1For linear alkene base, M2It is each independently hydrogen atom, methyl, ethyl, methoxyl group, ethyoxyl；
(2) toward the alcohol compound added in the haloalkenyl group phenol compound A made from step (1) as catalyst,
It is slowly introducing ammonia, and stirring reaction 60min~120min；After completion of the reaction, add glacial acetic acid and adjust pH value to neutrality, be made
Amino substituted alkenyl phenol compound B；
(3) using the amino substituted alkenyl phenol compound B made from step (2) as end group reactant, it is anti-to be placed in pressurization
Answer in device, and add anionic ring-opening polymerization catalysts and oxirane (EO) or expoxy propane (PO), 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, anionic ring-opening polymerization reaction
After completely, less than 55 DEG C are cooled the temperature to, glacial acetic acid is added and adjusts pH value to 6.5~7.5, the unsaturated polyoxy second is made
Alkene ether derivant.
2. the synthetic method of unsaturated polyoxyethylene ether derivant according to claim 1, it is characterised in that the halogen
Gas is chlorine or bromine vapor or iodine vapor.
3. the synthetic method of unsaturated polyoxyethylene ether derivant according to claim 1, it is characterised in that the alkenyl
Phenol compound is selected from following any：4- pi-allyls -2,6- syringol, trans -2- ethyoxyls -5- (1- propylene
Base) phenol, 2- pi-allyl -6- methylphenols.
4. the synthetic method of unsaturated polyoxyethylene ether derivant according to claim 1, it is characterised in that the straight chain
Alkylene is following any：Vinyl, acrylic, 1- cyclobutenyls, 2- cyclobutenyls.
5. the synthetic method of unsaturated polyoxyethylene ether derivant according to claim 1, it is characterised in that the alcohols
Compound is following any：Methanol, ethanol or propyl alcohol.
6. the synthetic method of unsaturated polyoxyethylene ether derivant according to claim 1, it is characterised in that it is described it is cloudy from
Sub- ring-opening polymerization catalyst is selected from following any：Sodium methoxide, potassium methoxide, caustic alcohol, potassium ethoxide.
A kind of 7. unsaturated polyoxyethylene ether derivant made from synthetic method according to any of the above-described claim.
8. a kind of preparation method of Early-strength polycarboxylate superplasticizer, it is characterised in that using as claimed in claim 7 unsaturated
Polyoxyethylene ether derivant is a kind of reaction raw materials, with unsaturated carboxylic acid, and other unsaturations with copolyreaction activity
Compound carries out free radicals copolymerization reaction, synthesizes the Early-strength polycarboxylate superplasticizer.
A kind of 9. Early-strength polycarboxylate superplasticizer synthesized using preparation method as claimed in claim 8.
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| 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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