CN109705332A - A kind of both sexes unsaturated polyether and the preparation method and application thereof - Google Patents
A kind of both sexes unsaturated polyether and the preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to technical field of concrete additives, in particular to a kind of both sexes unsaturated polyether, and it is related to the preparation method of the both sexes unsaturated polyether, further relate to application of the both sexes unsaturated polyether in production polycarboxylate water-reducer.The both sexes unsaturated polyether, has following structure general formula:, R1、R2、R3It is each independently selected from the alkyl of H or C1~C3；R4、R5It is each independently selected from the alkyl of C1~C8；X is ketone group or carbonyl；A is alkoxyl oxygen alkyl ethyl；B is alkoxyl propyl；M, n is each independently selected from 1~100 integer.Be conducive to further synthesize new polycarboxylate water-reducer according to both sexes unsaturated polyether made from the preparation method, after above-mentioned new polycarboxylate water-reducer is applied to concrete, the slump/divergence and compression strength of the concrete are remarkably reinforced.
Description
Technical field
The invention belongs to technical field of concrete additives, in particular to a kind of both sexes unsaturated polyether, and be related to this two
Property unsaturated polyether preparation method, further relate to the both sexes unsaturated polyether production polycarboxylate water-reducer in application.
Background technique
Concrete is the widest construction material of modern Application, super-huge to build with constantly bringing forth new ideas for Architectural Design
It is increasingly sophisticated to build engineering, terrestrial reference type Architectural Structure Design, more stringent requirements are proposed to concrete technology and construction method.Many institutes
Known, polycarboxylate water-reducer is one of key foundation and motive force of the development of modern concrete technology.
With the continuous expansion of polycarboxylate water-reducer application field, concrete also proposed the performance of polycarboxylate water-reducer
Higher requirement, on the one hand, high-strength, superelevation is strong, low water binder ratio concrete technology is gradually promoted, on the other hand, concrete former material
Expect that growing tension, quality are worsening, the water-reducing rate of high water reduction type polycarboxylate water-reducer originally has been unable to meet concrete and wants
It asks.Therefore, under current application situation, need to develop that a kind of water-reducing rate is higher, polycarboxylate water-reducer of better adaptability.
Polycarboxylate water-reducer in the market be usually with terminal double bond end alkenyl polyoxyethylene ether polymeric monomer with not
What the small molecule monomers such as saturated carboxylic acid were synthesized in a manner of combined polymerization under initiator effect.Correlative study the result shows that, polycarboxylic acids
The diminishing peptizaiton of water-reducing agent depends on the electrostatic reprimand formed after the anionic groups such as carboxylic acid, sulfonic acid absorption cement granules
Power and the effect of the steric hindrance of polyethylene oxide side chains.Currently, the unsaturated polyether of the domestic synthesis for polycarboxylate water-reducer is big
Monomer specifically includes that four based on TPEG (isopentene group polyoxyethylene ether) and HPEG (methyl allyl alcohol polyoxyethylene ether)
Carbon, five carbon type polyether macromonomers.However, since the small molecule monomers polymerization reaction such as such polyether macromonomer and carboxylic acid, sulfonic acid is living
Property there are significant difference, this results in the water-reducing agent Molecular Adsorption group of synthesis and polyethylene oxide side chains distribution, and there is very big
Inhomogeneities, and polyethylene oxide side chains chain link does not have absorption property, to cause polycarboxylate water-reducer molecule in cement
There is one tilting of an absorption or the intermediate bad phenomenon tilted of both ends absorption in the absorption on grain surface, therefore reduces poly- carboxylic
The absorption dispersion efficiency of sour diminishing agent molecule.
Summary of the invention
The present invention is directed to overcome above-mentioned technological deficiency existing in the prior art, and provides and a kind of can inherently be adsorbed in water
The both sexes unsaturated polyether of mud particle surface further obtains the ideal polycarboxylate water-reducer of performance based on this.Pass through one
Serial experiment confirms, shows superior dispersion performance using the polycarboxylate water-reducer that the both sexes unsaturated polyether produces, and
The working performance for the concrete being administered can be significantly improved.
Specifically, the first aspect of the present invention provides a kind of both sexes unsaturated polyether, has following structure general formula:
Wherein, R1、R2、R3It is each independently selected from the alkyl of H or C1~C3；R4、R5It is each independently selected from C1~C8's
Alkyl；X is ketone group or carbonyl；A is alkoxyl oxygen alkyl ethyl；B is alkoxyl propyl；M, n is each independently selected from 1~100 integer.
Preferably, in the both sexes unsaturated polyether, R1、R2、R3It is each independently H or methyl；R4、R5It is respectively independent
Ground is selected from the alkyl of C1~C3；And m is selected from 20~50 integer, n is selected from 1~10 integer.
Preferably, the molecular weight of the both sexes unsaturated polyether is 1000~5000Da.
Wherein, which can pass through unsaturated phosphoramidate containing double bonds as a kind of polymeric monomer
Alkoxylate occurs under the catalyst action of appropriate type to be polymerized.
Therefore, second aspect of the present invention provides the preparation method of the both sexes unsaturated polyether comprising following steps:
S1: under inert gas shielding, by unsaturated phosphoramidate containing double bonds and ferric trichloride/dicyanogen methyl isophorone cobalt acid zinc
The composite catalyst of complex composition is added into autoclave together, is warming up to 100~120 DEG C, and to the reaction under high pressure
First part's ethylene oxide is added in kettle and carries out pre-reaction；
S2: after pre-reaction, second part ethylene oxide, propylene oxide are added into the autoclave, and 130
The reaction was continued under conditions of~150 DEG C and 0.3~0.5MPa；
S3: implement heat preservation slaking reaction at 130~140 DEG C；
S4: reaction system is cooled to 70 DEG C, the unreacted impurity of vacuum removal, acid adding neutralizes to get the both sexes not
It is saturated polyethers.
Wherein, the inert gas can be nitrogen or argon gas.
Preferably, in the above preparation method, the ferric trichloride/dicyanogen methyl isophorone cobalt acid Zn complex composition composite catalyzing
The quality of agent is the 0.2%~3% of the quality of the unsaturated phosphoramidate containing double bonds.
It is further preferred that in the above preparation method, the ferric trichloride/dicyanogen methyl isophorone cobalt acid Zn complex composition is answered
The quality of conjunction catalyst is the 0.5%~2% of the quality of the unsaturated phosphoramidate containing double bonds.
Preferably, in the above preparation method, the acid is selected from following any one or more combination: acetic acid, formic acid, benzene
Formic acid.
Further, since in view of bring gassiness when the both sexes unsaturated polyether polymeric monomer is synthesized for polycarboxylate water-reducer
Amount variation, propylene oxide should not be used alone.It is therefore preferred that in the above preparation method, first part's ethylene oxide
With the quality sum of the second part ethylene oxide, with the quality of the propylene oxide the ratio between be 2:1~8:1.
Preferably, in the above preparation method, the synthesis step of the unsaturated phosphoramidate containing double bonds includes:
P1: equimolar unsaturated ammonia components, formaldehyde, alkyl phosphonium chloride component are added into reaction vessel, and resistance is added
Then poly- agent and organic acid catalyst are reacted at 70~110 DEG C；
P2: vacuum distillation removes impurity to get the unsaturated phosphoramidate containing double bonds；
Wherein, the unsaturated ammonia components are selected from following any one or more combination: acrylamide, methacryl
Amine, crotonamide, methyl butene amide, dimethylaminoethyl methyl esters, methacrylic acid lignocaine methyl esters, acrylic acid
Dimethylamino methyl esters, acrylic acid lignocaine methyl esters；
Wherein, the alkyl phosphonium chloride group is selected from following any one or more combination: dimethylammonium chloride phosphine, diethyl
Phosphonium chloride, dipropyl phosphonium chloride.
It can be seen that the unsaturated phosphoramidate containing double bonds can be by unsaturated ammonia components, formaldehyde, alkyl chlorination
Phosphine component occurs a step condensation reaction and forms.
It is further preferred that in the above preparation method, the polymerization inhibitor is selected from following any one or more combination: right
Benzenediol, p-tert-Butylcatechol, p-methyl phenol；Also, the quality of the polymerization inhibitor is the unsaturated ammonia components
The 0.1%~3% of quality.
It is further preferred that in the above preparation method, the quality of the polymerization inhibitor is the unsaturated ammonia components
The 0.5%~1% of quality.
It is further preferred that in the above preparation method, the organic acid catalyst is formic acid or/and acetic acid；Also, institute
State organic acid catalyst quality be the unsaturated ammonia components, the formaldehyde, the alkyl phosphonium chloride component gross mass
1%~5%.
It is further preferred that in the above preparation method, the quality of the organic acid catalyst is the unsaturated ammonia
Component, the formaldehyde, the alkyl phosphonium chloride component gross mass 1.5%~3%.
Meanwhile third aspect present invention provides both sexes unsaturated polyether described in first aspect in production polycarboxylic acids diminishing
Application in agent, wherein the both sexes unsaturated polyether and unsaturated carboxylic acid carry out free radicals copolymerization reaction so that polycarboxylic acids is made
Water-reducing agent.Due in this application, polycarboxylate water-reducer be it is obtained in conventional manner, therefore, relevant concrete operation step
It will not repeat herein.
Therefore, compared with prior art, the invention has the following beneficial technical effects:
Firstly, using unsaturated ammonia components, formaldehyde, alkyl phosphonium chloride component institute can be synthesized by a step condensation reaction
State unsaturated phosphoramidate containing double bonds；Especially, which only need to be by simple vacuum distillation operation to remove impurity elimination
Matter, without further purifying, so that it may which directly participation next step alkoxylation, technique are environmentally protective.Secondly, according to this hair
The preparation method of both sexes unsaturated polyether, has been successfully introduced into amino and phosphate in unsaturated monomer provided by bright, according to
Be conducive to further synthesize new polycarboxylate water-reducer according to both sexes unsaturated polyether made from the preparation method, and make the poly- carboxylic
The polyether chain energy conservation of sour water-reducing agent is directly adsorbed in cement particle surface, and this improves the uses of polycarboxylate water-reducer molecule
Efficiency, to significantly enhance the dispersion performance and working performance of concrete of polycarboxylate water-reducer.Finally, passing through a series of realities
Verifying is real, after above-mentioned new polycarboxylate water-reducer is applied to concrete, the slump/divergence of the concrete, and Yi Jikang
Compressive Strength is remarkably reinforced.
Specific embodiment
The present invention is further elaborated With reference to embodiment, but the present invention is not limited to following embodiment party
Formula.
A kind of preparation method of both sexes unsaturated polyether according to a preferred embodiment of the present invention comprising following step
It is rapid:
S1: unsaturated phosphoramidate containing double bonds is answered with ferric trichloride/dicyanogen methyl isophorone cobalt acid Zn complex composition
It closes catalyst to be added into autoclave together, falls the air in reaction kettle with inert gas replacement after mixing, then
100~120 DEG C are warming up to, and first part's ethylene oxide is added into the autoclave and carries out pre-reaction, when the pre-reaction
Between about 30 minutes；
S2: after pre-reaction, second part ethylene oxide, propylene oxide are added into the autoclave, and 130
The reaction was continued under conditions of~150 DEG C and 0.3~0.5MPa；
S3: implement heat preservation slaking reaction at 130~140 DEG C, until the pressure in the autoclave is no longer fallen to
Only；
S4: reaction system is cooled to 70 DEG C, the unreacted impurity of vacuum removal, acid adding neutralizes to get the both sexes not
It is saturated polyethers.
In a preferred embodiment, the composite catalyst that the ferric trichloride/dicyanogen methyl isophorone cobalt acid Zn complex forms
Quality is the 0.2%~3% of the quality of the unsaturated phosphoramidate containing double bonds.
In a preferred embodiment, the acid is selected from following any one or more combination: acetic acid, formic acid, benzoic acid.
In a preferred embodiment, the quality of first part's ethylene oxide and the second part ethylene oxide it
With, with the quality of the propylene oxide the ratio between be 2:1~8:1.
In a preferred embodiment, the synthesis step of the unsaturated phosphoramidate containing double bonds includes:
P1: equimolar unsaturated ammonia components, formaldehyde, alkyl phosphonium chloride component are added into reaction vessel, and resistance is added
Then poly- agent and organic acid catalyst are stirred to react 5~8 hours at 70~110 DEG C；
P2: vacuum distillation removes impurity to get the unsaturated phosphoramidate containing double bonds；
Wherein, the unsaturated ammonia components are selected from following any one or more combination: acrylamide, methacryl
Amine, crotonamide, methyl butene amide, dimethylaminoethyl methyl esters, methacrylic acid lignocaine methyl esters, acrylic acid
Dimethylamino methyl esters, acrylic acid lignocaine methyl esters；
Wherein, the alkyl phosphonium chloride group is selected from following any one or more combination: dimethylammonium chloride phosphine, diethyl
Phosphonium chloride, dipropyl phosphonium chloride.
In a further preferred embodiment, the polymerization inhibitor is selected from following any one or more combination: to benzene
Diphenol, p-tert-Butylcatechol, p-methyl phenol；Also, the quality of the polymerization inhibitor is the matter of the unsaturated ammonia components
The 0.1%~3% of amount.
In a further preferred embodiment, the organic acid catalyst is formic acid or/and acetic acid；Also, it is described
The quality of organic acid catalyst be the unsaturated ammonia components, the formaldehyde, the alkyl phosphonium chloride component gross mass 1%
~5%.
Operation in following embodiments is routine operation unless otherwise instructed, and described device, reagent etc. are especially said such as nothing
It is bright equal to be bought from public commercial source.
Embodiment 1
I. the synthesis of unsaturated phosphoramidate containing double bonds
1mol acrylamide, 1mol formaldehyde, 1mol dimethylammonium chloride phosphine are placed in reaction vessel, stirred evenly, is added
0.71g p-methyl phenol, 3.20g glacial acetic acid continue stirring and are warming up to 85 DEG C, react 6 hours.Vacuum distillation removes impurity, obtains
To unsaturated phosphoramidate (S1-1) containing double bonds.
II. the synthesis of both sexes unsaturated polyether
Unsaturation phosphoramidate (S1-1) 500g containing double bonds and ferric trichloride 0.5g, dicyanogen methyl isophorone cobalt acid zinc are cooperated
Object 2.5g is placed in autoclave, is displaced the air in autoclave with nitrogen after mixing, is then heated to 100
~120 DEG C, and the ethylene oxide that 163g is added carries out pre-reaction, pre-reaction time was controlled at 30 minutes.
Continue that ethylene oxide 1834g, propylene oxide 1439g are added into the autoclave after pre-reaction, reaction
At 130~150 DEG C, reaction pressure is controlled in 0.3~0.5MPa for temperature control.
Then, heat preservation curing is carried out at 130~140 DEG C, until the pressure in reaction kettle no longer declines.
Reaction system is cooled to 70 DEG C, the unreacted impurity of vacuum removal, add formic acid neutralize to obtain both sexes unsaturation it is poly-
Ether polymeric monomer (S1-2), through detecting, molecular weight 1270Da.
Embodiment 2
I. the synthesis of unsaturated phosphoramidate containing double bonds
Specific synthesis step is same as Example 1.
II. the synthesis of both sexes unsaturated polyether
By unsaturation phosphoramidate (S1-1) 500g containing double bonds and ferric trichloride 1g, dicyanogen methyl isophorone cobalt acid Zn complex
3.5g is placed in autoclave, displaces the air in autoclave with nitrogen after mixing, then heat to 100~
120 DEG C, and the ethylene oxide that 352g is added carries out pre-reaction, pre-reaction time was controlled at 30 minutes.
Continue that ethylene oxide 5484g, propylene oxide 1563g are added into the autoclave after pre-reaction, reaction
At 130~150 DEG C, reaction pressure is controlled in 0.3~0.5MPa for temperature control.
Then, heat preservation curing is carried out at 130~140 DEG C, until the pressure in reaction kettle no longer declines.
Reaction system is cooled to 70 DEG C, the unreacted impurity of vacuum removal, add formic acid neutralize to obtain both sexes unsaturation it is poly-
Ether polymeric monomer (S2-2), through detecting, molecular weight 2531Da.
Embodiment 3
I. the synthesis of unsaturated phosphoramidate containing double bonds
1mol Methacrylamide, 1mol formaldehyde, 1mol dimethylammonium chloride phosphine are placed in reaction vessel, stirred evenly,
0.42g p-methyl phenol, 5.20g glacial acetic acid is added, continues stirring and is warming up to 90 DEG C, react 7 hours.Vacuum distillation removes impurity elimination
Matter obtains unsaturated phosphoramidate (S3-1) containing double bonds.
II. the synthesis of both sexes unsaturated polyether
By unsaturation phosphoramidate (S3-1) 500g containing double bonds and ferric trichloride 1g, dicyanogen methyl isophorone cobalt acid Zn complex
2.5g is placed in autoclave, displaces the air in autoclave with nitrogen after mixing, then heat to 100~
110 DEG C, and the ethylene oxide that 123g is added carries out pre-reaction, pre-reaction time was controlled at 30 minutes.
Continue that ethylene oxide 1992g, propylene oxide 345g are added into the autoclave after pre-reaction, reaction temperature
At 130~140 DEG C, reaction pressure is controlled in 0.35~0.45MPa for degree control.
Then, heat preservation curing is carried out at 130~135 DEG C, until the pressure in reaction kettle no longer declines.
Reaction system is cooled to 70 DEG C, the unreacted impurity of vacuum removal, add formic acid neutralize to obtain both sexes unsaturation it is poly-
Ether polymeric monomer (S3-2), through detecting, molecular weight 1340Da.
Embodiment 4
I. the synthesis of unsaturated phosphoramidate containing double bonds
1mol dimethylaminoethyl methyl esters, 1mol formaldehyde, 1mol dimethylammonium chloride phosphine are placed in reaction vessel,
It stirs evenly, 2.37g p-methyl phenol, 5.20g glacial acetic acid is added, continue stirring and be warming up to 90 DEG C, react 6 hours.Decompression is steamed
Distillation decontamination obtains unsaturated phosphoramidate (S4-1) containing double bonds.
II. the synthesis of both sexes unsaturated polyether
By unsaturation phosphoramidate (S4-1) 500g containing double bonds and ferric trichloride 1g, dicyanogen methyl isophorone cobalt acid Zn complex
2.5g is placed in autoclave, displaces the air in autoclave with nitrogen after mixing, then heat to 100~
110 DEG C, and the ethylene oxide that 228g is added carries out pre-reaction, pre-reaction time was controlled at 30 minutes.
Continue that ethylene oxide 4141g, propylene oxide 694g are added into the autoclave after pre-reaction, reaction temperature
At 130~140 DEG C, reaction pressure is controlled in 0.35~0.45MPa for degree control.
Then, heat preservation curing is carried out at 130~135 DEG C, until the pressure in reaction kettle no longer declines.
Reaction system is cooled to 70 DEG C, the unreacted impurity of vacuum removal, add acetic acid neutralize to obtain both sexes unsaturation it is poly-
Ether polymeric monomer (S4-2), through detecting, molecular weight 2320Da.
Embodiment 5
I. the synthesis of unsaturated phosphoramidate containing double bonds
Specific synthesis step is same as Example 4.
II. the synthesis of both sexes unsaturated polyether
By unsaturation phosphoramidate (S4-1) 500g containing double bonds and ferric trichloride 2g, dicyanogen methyl isophorone cobalt acid Zn complex
4.5g is placed in autoclave, displaces the air in autoclave with nitrogen after mixing, then heat to 110~
120 DEG C, and the ethylene oxide that 228g is added carries out pre-reaction, pre-reaction time was controlled at 30 minutes.
Continue that ethylene oxide 3950g, propylene oxide 885g are added into the autoclave after pre-reaction, reaction temperature
At 140~150 DEG C, reaction pressure is controlled in 0.3~0.4MPa for degree control.
Then, heat preservation curing is carried out at 130~135 DEG C, until the pressure in reaction kettle no longer declines.
Reaction system is cooled to 70 DEG C, the unreacted impurity of vacuum removal, add acetic acid neutralize to obtain both sexes unsaturation it is poly-
Ether polymeric monomer (S5-2), through detecting, molecular weight 2230Da.
Embodiment 6
I. the synthesis of unsaturated phosphoramidate containing double bonds
1mol dimethylaminoethyl methyl esters, 1mol formaldehyde, 1mol diethyl phosphonium chloride are placed in reaction vessel,
It stirs evenly, 2.37g p-methyl phenol, 6.20g glacial acetic acid is added, continue stirring and be warming up to 110 DEG C, react 6 hours.Decompression is steamed
Distillation decontamination obtains unsaturated phosphoramidate (S6-1) containing double bonds.
II. the synthesis of both sexes unsaturated polyether
By unsaturation phosphoramidate (S6-1) 500g containing double bonds and ferric trichloride 2g, dicyanogen methyl isophorone cobalt acid Zn complex
4.5g is placed in autoclave, displaces the air in autoclave with argon gas after mixing, then heat to 100~
120 DEG C, and the ethylene oxide that 239g is added carries out pre-reaction, pre-reaction time was controlled at 30 minutes.
Continue that ethylene oxide 3889g, propylene oxide 652g are added into the autoclave after pre-reaction, reaction temperature
At 130~150 DEG C, reaction pressure is controlled in 0.35~0.45MPa for degree control.
Then, heat preservation curing is carried out at 130~135 DEG C, until the pressure in reaction kettle no longer declines.
Reaction system is cooled to 70 DEG C, the unreacted impurity of vacuum removal, add acetic acid neutralize to obtain both sexes unsaturation it is poly-
Ether polymeric monomer (S6-2), through detecting, molecular weight 2436Da.
Embodiment 7
I. the synthesis of unsaturated phosphoramidate containing double bonds
1mol dimethylaminoethyl methyl esters, 1mol formaldehyde, 1mol diethyl phosphonium chloride are placed in reaction vessel,
It stirs evenly, 2.37g p-methyl phenol, 6.20g glacial acetic acid is added, continue stirring and be warming up to 85 DEG C, react 6 hours.Decompression is steamed
Distillation decontamination obtains unsaturated phosphoramidate (S7-1) containing double bonds.
II. the synthesis of both sexes unsaturated polyether
By unsaturation phosphoramidate (S7-1) 500g containing double bonds and ferric trichloride 3g, dicyanogen methyl isophorone cobalt acid Zn complex
3.5g is placed in autoclave, displaces the air in autoclave with argon gas after mixing, then heat to 100~
120 DEG C, and the ethylene oxide that 239g is added carries out pre-reaction, pre-reaction time was controlled at 30 minutes.
Continue that ethylene oxide 2815g, propylene oxide 1726g are added into the autoclave after pre-reaction, reaction
At 130~150 DEG C, reaction pressure is controlled in 0.3~0.5MPa for temperature control.
Then, heat preservation curing is carried out at 130~140 DEG C, until the pressure in reaction kettle no longer declines.
Reaction system is cooled to 70 DEG C, the unreacted impurity of vacuum removal, add acetic acid neutralize to obtain both sexes unsaturation it is poly-
Ether polymeric monomer (S7-2), through detecting, molecular weight 2150Da.
In addition, inventor is also respectively with both sexes unsaturated polyether polymeric monomer (S1-2~S7-2), methallyl alcohol polyoxy second
Alkene ether (HPEG), isopentene group polyoxyethylene ether (TPEG) are reaction raw materials, have synthesized a variety of polycarboxylic acids by same reaction conditions
Water-reducing agent, and the measurement of correlated performance has been carried out, key index is compared.
Compression strength: according to pressure resistance in GB/T 50081-2002 " standard for test methods of mechanical properties of ordinary concrete "
Spend test method measurement.
The slump/divergence: according in GB/T 50080-2016 " Standard for test methods of properties of ordinary concrete mixture standard "
Test method measurement.
It after above-mentioned a variety of polycarboxylate water-reducers are applied to concrete, is measured, has according to each respective standard respectively
Body measurement result is as shown in table 1 below:
1 compression strength of table and the slump/divergence table of comparisons
By analyzing the data in upper table 1 it is found that opposite with the commercially available polycarboxylate water-reducer of conventional polyether monomer synthesis
Than, after applying polycarboxylate water-reducer new as made from both sexes unsaturated polyether polymeric monomer (S1-2~S7-2) in concrete,
The slump/the divergence and 7d/28d compression strength of the concrete, which are significantly better than that, applied commercially available polycarboxylate water-reducer
Concrete.
Therefore, higher diminishing is shown using polycarboxylate water-reducer made from both sexes unsaturated polyether of the present invention
Rate, superior workability and more longlasting stability.
Specific embodiments of the present invention are described in detail above, but it is only used as example, the present invention is not intended to limit
In particular embodiments described above.To those skilled in the art, it any equivalent modifications to the practical progress and replaces
In generation, is also all among scope of the invention.Therefore, without departing from the spirit and scope of the invention made by equal transformation and repair
Change, all should be contained within the scope of the invention.
Claims (9)
1. a kind of both sexes unsaturated polyether, which is characterized in that have following structure general formula:
Wherein, R1、R2、R3It is each independently selected from the alkyl of H or C1~C3；R4、R5It is each independently selected from the alkyl of C1~C8；
X is ketone group or carbonyl；A is alkoxyl oxygen alkyl ethyl；B is alkoxyl propyl；M, n is each independently selected from 1~100 integer.
2. a kind of preparation method of both sexes unsaturated polyether according to claim 1, which is characterized in that including following step
It is rapid:
S1: under inert gas shielding, unsaturated phosphoramidate containing double bonds and ferric trichloride/dicyanogen methyl isophorone cobalt acid zinc are cooperated
The composite catalyst of object composition is added into autoclave together, is warming up to 100~120 DEG C, and into the autoclave
First part's ethylene oxide is added and carries out pre-reaction；
S2: after pre-reaction, second part ethylene oxide, propylene oxide being added into the autoclave, and 130~
The reaction was continued under conditions of 150 DEG C and 0.3~0.5MPa；
S3: implement heat preservation slaking reaction at 130~140 DEG C；
S4: reaction system is cooled to 70 DEG C, the unreacted impurity of vacuum removal, acid adding neutralizes unsaturated to get the both sexes
Polyethers.
3. preparation method according to claim 2, which is characterized in that the ferric trichloride/dicyanogen methyl isophorone cobalt acid Zn complex
The quality of the composite catalyst of composition is the 0.2%~3% of the quality of the unsaturated phosphoramidate containing double bonds.
4. preparation method according to claim 2, which is characterized in that the acid is selected from following any one or more group
It closes: acetic acid, formic acid, benzoic acid.
5. preparation method according to claim 2, which is characterized in that first part's ethylene oxide and described second
The quality sum of point ethylene oxide, with the quality of the propylene oxide the ratio between be 2:1~8:1.
6. preparation method according to claim 2, which is characterized in that the unsaturated phosphoramidate containing double bonds
Synthesis step includes:
P1: equimolar unsaturated ammonia components, formaldehyde, alkyl phosphonium chloride component are added into reaction vessel, and polymerization inhibitor is added
And organic acid catalyst, then reacted at 70~110 DEG C；
P2: vacuum distillation removes impurity to get the unsaturated phosphoramidate containing double bonds；
Wherein, the unsaturated ammonia components are selected from following any one or more combination: acrylamide, Methacrylamide, fourth
Acrylamide, methyl butene amide, dimethylaminoethyl methyl esters, methacrylic acid lignocaine methyl esters, acrylic acid diformazan
Amino methyl, acrylic acid lignocaine methyl esters；
Wherein, the alkyl phosphonium chloride group is selected from following any one or more combination: dimethylammonium chloride phosphine, diethyl chlorination
Phosphine, dipropyl phosphonium chloride.
7. preparation method according to claim 6, which is characterized in that the polymerization inhibitor is selected from following any one or more
Combination: hydroquinone, p-tert-Butylcatechol, p-methyl phenol；Also, the quality of the polymerization inhibitor is the unsaturated ammonia
The 0.1%~3% of the quality of component.
8. preparation method according to claim 6, which is characterized in that the organic acid catalyst is formic acid or/and acetic acid；
Also, the quality of the organic acid catalyst be the unsaturated ammonia components, the formaldehyde, the alkyl phosphonium chloride component it is total
The 1%~5% of quality.
9. application of the both sexes unsaturated polyether according to claim 1 in production polycarboxylate water-reducer, which is characterized in that
The both sexes unsaturated polyether and unsaturated carboxylic acid carry out free radicals copolymerization reaction so that polycarboxylate water-reducer is made.
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| CN111040146A (en) * | 2019-12-05 | 2020-04-21 | 上海台界化工有限公司 | Synthesis method of phosphorus-containing unsaturated polyoxyethylene ether, product and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20140163161A1 (en) * | 2011-09-06 | 2014-06-12 | Sika Technology Ag | Comb polymers with delayed alkaline hydrolysis |
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| CN107337767A (en) * | 2016-12-30 | 2017-11-10 | 江苏苏博特新材料股份有限公司 | A kind of preparation method of the water reducer of phosphorous acid groups |
| CN108975747A (en) * | 2018-08-01 | 2018-12-11 | 上海台界化工有限公司 | A kind of synthetic method of slow-setting polycarboxylic acid water reducing agent |
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| US20140163161A1 (en) * | 2011-09-06 | 2014-06-12 | Sika Technology Ag | Comb polymers with delayed alkaline hydrolysis |
| CN105482095A (en) * | 2015-12-22 | 2016-04-13 | 南京红宝丽聚氨酯有限公司 | Unsaturated polyether alcohol and polycarboxylate water reducer prepared by same |
| CN107337767A (en) * | 2016-12-30 | 2017-11-10 | 江苏苏博特新材料股份有限公司 | A kind of preparation method of the water reducer of phosphorous acid groups |
| CN108975747A (en) * | 2018-08-01 | 2018-12-11 | 上海台界化工有限公司 | A kind of synthetic method of slow-setting polycarboxylic acid water reducing agent |
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| CN111040146A (en) * | 2019-12-05 | 2020-04-21 | 上海台界化工有限公司 | Synthesis method of phosphorus-containing unsaturated polyoxyethylene ether, product and application thereof |
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