CN105646867B - A kind of alkenyl carbonic acid ester polyether and preparation method and application - Google Patents
A kind of alkenyl carbonic acid ester polyether and preparation method and application Download PDFInfo
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Abstract
The invention provides a kind of alkenyl carbonic acid ester polyether, has following structure：Wherein, wherein, R1For H or C1~C3Alkyl；R2For C1~C5Alkylidene；R3For C2~C4Alkylidene, phenylene or benzal；M is to include construction unit CH2CH2O‑、‑CH(CH3)CH2O‑、‑CH2(CH3) one or more polyether chains in CHO.Contain carbonate group in the alkenyl carbonic acid ester polyether of the present invention, be advantageous to strengthen strand toughness, so as to strengthen the steric hindrance effect of synthesis diminishing agent molecule, carbonate group adds the side chain density of synthesis water reducer in addition, is advantageous to improve the dispersive property of water reducer；Carbonate group has stronger electronegativity in polyethers so that manufactured water reducer has certain anti-stick mud suction-operated.And the polyethers of the present invention is nontoxic, easily degraded, environmentally friendly.
Description
Technical field
The present invention relates to a kind of alkenyl carbonic acid ester polyether and its preparation method and application, is specially that one kind is used to prepare poly- carboxylic
Alkenyl carbonic acid ester polyether of sour water reducer and preparation method thereof.
Background technology
With the fast development of China's economy, infrastructure construction paces are accelerated, the ecology and height of concrete admixture
Performance-based requires also more and more urgent.The research and application of concrete admixture improve construction engineering quality while also promoted
An important portion in the research and application of the progress of construction technology, especially high efficiency water reducing agent even more architectural materials science research
Point, and promote construction material to be continued to develop to high-strength, high performance, wherein using polycarboxylic acid series high efficiency water reducing agent as representative, into
For the important component of new generation of green high efficiency water reducing agent, the adjustable degree of its molecular structure is bigger, can be matched somebody with somebody according to specific requirement
Put out the water reducer of different performance.
End alkylene polyalkoxy ether or ester are the principal monomers of polycarboxylate water-reducer synthesis, and common monomer is carbon number
3-5 enol ether or ester.With the fast development of concrete industry, the water reducer performance of conventional monomeric synthesis can not meet should
With needs.Development function, the polyether monomer of differentiation are urgently to be resolved hurrily as industry to synthesize the water reducer for meeting different demands
The problem of.
The content of the invention
To solve the above problems, the invention provides a kind of alkenyl carbonic acid ester polyether, there is following structure：
Wherein, R1For H or C1~C3Alkyl；R2For C1~C5Alkylidene；R3For C2~C4Alkylidene, phenylene or
Benzal；M is to include construction unit-CH2CH2O-、-CH(CH3)CH2O-、-CH2(CH3) one or more polyethers in CHO-
Chain.
According to an embodiment of the present invention, the alkenyl carbonic acid ester polyether is that homopolymer, random copolymer or block are total to
Polymers.
According to another embodiment of the present invention, the structure of the alkenyl carbonic acid ester polyether is：
Or
Wherein, m, n are integer, and 2≤m+n≤200.
According to another embodiment of the present invention, the number-average molecular weight of the alkenyl carbonic acid ester polyether is 250~10000.
According to another embodiment of the present invention, the number-average molecular weight of the alkenyl carbonic acid ester polyether is 1000~5000.
Present invention also offers a kind of preparation method of alkenyl carbonic acid ester polyether, including using alkenyl carbonic ester as initiator,
The ring-opening polymerization of oxirane and/or expoxy propane is carried out, the alkenyl carbonic acid ester polyether is made；The alkenyl carbonic ester
Structure it is as follows：
Wherein, R1For H or C1~C3Alkyl；R2For C1~C5Alkylidene；R3For C2~C4Alkylidene, phenylene or
Benzal.
According to an embodiment of the present invention, wherein the number-average molecular weight of the alkenyl carbonic acid ester polyether be 250~
10000。
Invention further provides the alkenyl carbonic acid ester polyether of any of the above-described answering in polycarboxylate water-reducer is prepared
With.
Contain carbonate group in the alkenyl carbonic acid ester polyether of the present invention, be advantageous to strengthen strand toughness, so as to strengthen
The steric hindrance effect of diminishing agent molecule is synthesized, carbonate group adds the side chain density of synthesis water reducer in addition, favorably
In the dispersive property for improving water reducer；Carbonate group has stronger electronegativity in polyethers so that manufactured water reducer has
Certain anti-stick mud suction-operated.And the polyethers of the present invention is nontoxic, easily degraded, environmentally friendly.
Embodiment
Below, alkenyl carbonic acid ester polyether of the invention, preparation method and applications are done in detail with reference to embodiment
Explanation：
The alkenyl carbonic acid ester polyether of the present invention, has following structure：
Wherein, R1The alkyl for being 1~3 for H or carbon number；R2The alkylidene for being 1~5 for carbon number；R3For carbon atom
Number is 2~4 alkylidene, phenylene or benzal；M is to include construction unit-CH2CH2O-、-CH(CH3)CH2O-、-CH2
(CH3) one or more polyether chains in CHO-.
The alkenyl carbonic acid ester polyether of the present invention can be oxirane and/or expoxy propane through homopolymerization made from ring-opening polymerisation
Thing, such as PEO or PPOX；Can also be both block copolymers or random copolymer.
In one embodiment of the present invention, the number-average molecular weight of alkenyl carbonic acid ester polyether is 250-10000, preferably molecule
Measure as 1000-5000.
The alkenyl carbonic acid ester polyether of the present invention can carry out oxirane and/or epoxy third using alkenyl carbonic ester as initiator
The ring-opening polymerization of alkane is made；The structure of the alkenyl carbonic ester is as follows：
Wherein, R1The alkyl for being 1~3 for H or carbon number；R2The alkylidene for being 1~5 for carbon number；R3For carbon atom
Number is 2~4 alkylidene, phenylene or benzal.
Wherein, carbonic ester can be carried out obtained by ester exchange reaction by dimethyl carbonate and alcohol, phenol, and the alcohol can be carbon atom
Number is the straight diol that 3~10 straight or branched end alkenyl alcohol or carbon number are 2~4 or two containing phenyl ring
Alcohol, such as p-Hydroxybenzylalcohol.Above-mentioned phenol can be hydroquinones.
Invention further provides a kind of preparation method of alkenyl carbonic acid ester polyether, step are as follows：In high-pressure reactor
It is middle to add appropriate initiator and catalyst (determines the minimum addition of initiator according to the size of reactor and proportioning situation
Amount, catalytic amount are the 0.01~0.2% of output), water-tight equipment, nitrogen displacement afterwards, heating, when temperature reaches 80~
A small amount of epoxyalkane raw material is passed through at 130 DEG C, illustrates initiation reaction when temperature rise pressure declines, is passed through proportional quantity (root afterwards
Determined according to the raw material of different molecular weight) epoxyalkane raw material, controlling reaction temperature in 60~180 DEG C and kettle pressure 0.2
~0.6MPa, question response finish, pressure gradually decreases down continuous 30 minutes in kettle no longer decline after, aging cooling discharge, both
The polyethers.Wherein, initiator can be carbonic ester；Catalyst can be KOH or NaOH；Epoxyalkane can be oxirane
And/or expoxy propane (PO) (EO).
In one embodiment of the present invention, R1For CH3, R2For (CH2)4, R3For benzal, the synthesis of the structure is by carbonic acid
Dimethyl ester is carried out obtained by ester exchange reaction with alcohol, phenol.I.e. using 1- alkenyl -2- methyl cyclohexanols and p-Hydroxybenzylalcohol and carbonic acid two
Methyl esters carries out ester exchange reaction.The reaction comprises the following steps：(1) opens stirring in the reactor for possessing condition of negative pressure,
Add dimethyl carbonate and catalyst, catalyst can be solid acid or base catalyst, such as sulfuric acid, sodium methoxide or
Other catalyst well known in the art；(2) is to slowly warm up to 80~90 DEG C, and two kinds of alcohols materials of double dropwise additions are reacted, with
The progress of reaction, constantly has methanol to be discharged from system, treats that methanol no longer flows out, as reaction terminating；(3) cools, discharging；
(4) carries out vacuum distillation processing to product, separates target product and accessory substance, obtain mesh according to the difference of reaction product boiling point
Product is marked, its structure is shown below.
In one embodiment of the present invention, using the compound of said structure as initiator, alkenyl carbonic acid ester polyether is prepared,
Preparation method comprises the following steps：
(1) initiator is added in high-pressure reactor and catalyst is (true according to the size of reactor and proportioning situation
Determine the minimum addition of initiator, catalytic amount is the 0.01~0.2% of output).
(2) water-tight equipment, nitrogen displacement, heating, a small amount of epoxyalkane is passed through when temperature reaches 100~120 DEG C afterwards
Raw material, illustrate initiation reaction when temperature rise pressure declines, be passed through the epoxyalkane raw material of ormal weight, controlling reaction temperature afterwards
Pressure is in 0.3~0.5MPa in 110~130 DEG C and kettle.
(3) question response finishes, in kettle pressure gradually decrease down continuous 30 minutes no longer decline after, aging cooling discharge, both
Obtain the polyethers.
Wherein, catalyst can be KOH or NaOH or other catalyst well known in the art.
The alkenyl carbonic acid ester polyether end of the present invention has double bond, can be used for synthesizing polycarboxylic acid water reducing agent, the alkenyl
The initiator segment of polyethers contains carbonate group, is advantageous to strengthen strand toughness, so as to strengthen synthesis diminishing agent molecule
Steric hindrance acts on, to improve the dispersive property of water reducer.
With reference to embodiment, the present invention is further illustrated, but the present invention is not limited to the following example, wherein,
It is commercially available prod for the reactant used in synthetic reaction and catalyst.The synthesis of water reducer uses freedom well known in the art
Base polymerization technique, is copolymerized in water solution system, and EVA is adjusted by adding the three, the 4th monomers in polymerization process
The polymerization activity of system, finally give the combed polycarboxylate water-reducer that number-average molecular weight is 5000~35000.
The index determining of alkenyl carbonic acid ester polyether refers to method of testing as defined in professional standard HG/T4490-2013；Polyethers
Molecular weight distribution using exclusion chromatography (GPC) determine；Double bond retention rate is surveyed according to method as defined in GB/T13892-2012
Determine iodine number, and by being calculated；Concrete mixing specified in water reducer dispersive property test reference GB/T50080-2002
Physical performance method of testing.The anti-mud performance test methods of water reducer refer to flow of cement mortar specified in GB/T 2419-2005
Assay method.
Embodiment 1
In the reactor for possessing condition of negative pressure, stirring is opened, adds dimethyl carbonate and sulfuric acid, it is to slowly warm up to 80~
It is 90 DEG C, double into reactor that 1- alkenyl -2- methyl cyclohexanols and p-Hydroxybenzylalcohol is added dropwise.Wherein, three kinds of feeding intake for reactant are rubbed
You are at ratio：Dimethyl carbonate:1- alkenyl -2- methyl cyclohexanols:P-Hydroxybenzylalcohol=1:1.5:1.5, catalyst charge is throwing
Expect the 0.2% of gross mass.With the progress of reaction, Methanol product is constantly discharged out of system, 20min after methanol no longer flows out
Cooling, discharging.According to boiling point difference, vacuum distillation processing is carried out to product, separating by-products, obtains carbonic ester initiator (formula
1)。
215g carbonic esters (formula 1) initiator and 1.0g KOH are added in high-pressure reactor.Water-tight equipment, nitrogen displacement 3
It is secondary.Stirring is opened, heating, oxirane (EO, 551g) and expoxy propane that 5g is mixed are passed through when temperature reaches 100 DEG C
(PO, 234g) raw material.After temperature rise pressure declines, continue to be slowly introducing the above-mentioned epoxyalkane raw material mixed, control
Reaction temperature in 110~130 DEG C and kettle pressure in 0.3~0.5MPa.After charging, treat that pressure gradually decreases down company in kettle
After continuous 30 minutes no longer decline, aging cooling discharge, random copolymerization ether JM-I, the wherein number-average molecular weight of the ether, molecule are obtained
The test result of amount distribution and double bond retention rate is shown in Table 1.
Obtained atactic polyether is synthesized into water reducer with monomers such as methacrylic acids, step is as follows：In the reactor, add
70g deionized waters and 120g monomers A (atactic polyether of the present embodiment synthesis), 18.5g monomers B (acrylic acid), are heated with stirring to
80 DEG C, initiator (3.1 ammonium persulfates and 20g aqueous mixtures) and monomer C (2.2g methylpropene sodium sulfonates and 20g is then added dropwise
Aqueous mixtures), time for adding 2.5h, reaction time 3.5h, reaction are cooled to normal temperature after terminating, with mass concentration 30%
The NaOH aqueous solution adjusts pH value to neutrality, discharging, both obtains high-performance polycarboxylic acids water reducing agent product J SJ-I, the correlation of the water reducer
The performance test results are shown in Table 2,3.
Embodiment 2
In the reactor for possessing condition of negative pressure, stirring is opened, adds dimethyl carbonate and sulfuric acid, it is to slowly warm up to 80~
It is 90 DEG C, double into reactor that 1- alkenyl -2- methyl cyclohexanols and p-Hydroxybenzylalcohol is added dropwise.Wherein, three kinds of feeding intake for reactant are rubbed
You are at ratio：Dimethyl carbonate:1- alkenyl -2- methyl cyclohexanols:P-Hydroxybenzylalcohol=1:1.5:1.5, catalyst charge is throwing
Expect the 0.2% of gross mass.With the progress of reaction, Methanol product is constantly discharged out of system, 20min after methanol no longer flows out
Cooling, discharging.According to boiling point difference, vacuum distillation processing is carried out to product, separating by-products, obtains carbonic ester initiator (formula
1)。
107g carbonic esters (formula 1) initiator and 1.5g KOH are added in high-pressure reactor.Water-tight equipment, nitrogen displacement 3
It is secondary.Stirring is opened, heating, epoxyalkane raw material (EO 730g, PO that 5g is mixed are passed through when temperature reaches 100 DEG C
163g), after temperature rise pressure declines, continue to be slowly introducing the epoxyalkane raw material mixed, controlling reaction temperature is 110
~120 DEG C with pressure in kettle in 0.3~0.5MPa.After charging, treat that pressure gradually decreases down continuous 30 minutes no longer in kettle
After decline, aging cooling discharge, random copolymerization ether JM-II is obtained, the wherein number-average molecular weight of the ether, molecular weight distribution etc. is tested
It the results are shown in Table 1.
Obtained atactic polyether is synthesized into water reducer with monomers such as methacrylic acids, step is as follows：In the reactor, add
70g deionized waters and 240g monomers A (atactic polyether of the present embodiment synthesis), 18.5g monomers B (acrylic acid), are heated with stirring to
80 DEG C, initiator (3.1 ammonium persulfates and 20g aqueous mixtures) and monomer C (2.2g methylpropene sodium sulfonates and 20g is then added dropwise
Aqueous mixtures), time for adding 2.5h, reaction time 3.5h, reaction are cooled to normal temperature after terminating, with mass concentration 30%
The NaOH aqueous solution adjusts pH value to neutrality, discharging, both obtains high-performance polycarboxylic acids water reducing agent product J SJ-II, the correlation of the water reducer
The performance test results are shown in Table 2,3.
Embodiment 3
In the reactor for possessing condition of negative pressure, stirring is opened, dimethyl carbonate and sodium methoxide is added, is to slowly warm up to 80
It is~90 DEG C, double into reactor that 1- alkenyls amylalcohol and 1,3-PD is added dropwise.Wherein, the molar ratio of three kinds of reactants is：
Dimethyl carbonate:1- alkenyl amylalcohols:1,3- propane diols=1:1.5:1.5, catalyst charge is the 0.2% of gross mass of feeding intake.
With the progress of reaction, Methanol product is constantly discharged out of system, and 20min cools after methanol no longer flows out, discharging.According to boiling
Point difference, vacuum distillation processing is carried out to product, separating by-products, obtains carbonic ester initiator (formula 2).
176g carbonic esters (formula 2) initiator and 0.5g KOH are added in high-pressure reactor.Water-tight equipment, nitrogen displacement 3
It is secondary.Stirring is opened, heating, 5g oxirane is passed through when temperature reaches 100 DEG C, after temperature rise pressure declines, continues to delay
It is slow to be passed through oxirane (EO 823g) raw material, controlling reaction temperature in 110~130 DEG C and kettle pressure in 0.3~0.5MPa.
After charging, after pressure in kettle is gradually decreased down continuous 30 minutes and no longer declined, aging cooling discharge, polyethers JM- is obtained
III (formula 3), the test result of the number-average molecular weight of the ether, molecular weight distribution and double bond retention rate are shown in Table 1, wherein m=20.
Obtained polyethers is synthesized into water reducer with monomers such as methacrylic acids, step is as follows：In the reactor, 70g is added
Deionized water and 100g monomers A (atactic polyether of the present embodiment synthesis), 18.5g monomers B (acrylic acid), are heated with stirring to 80
DEG C, initiator (3.1 ammonium persulfates and 20g aqueous mixtures) and monomer C (2.2g methylpropene sodium sulfonates and 20g water is then added dropwise
Mixture), time for adding 2.5h, reaction time 3.5h, reaction are cooled to normal temperature after terminating, with mass concentration 30%
The NaOH aqueous solution adjusts pH value to neutrality, discharging, both obtains high-performance polycarboxylic acids water reducing agent product J SJ-III, the phase of the water reducer
Close the performance test results and be shown in Table 2.
Embodiment 4
In the reactor for possessing condition of negative pressure, stirring is opened, dimethyl carbonate and sodium methoxide is added, is to slowly warm up to 80
It is~90 DEG C, double into reactor that 1- alkenyls amylalcohol and 1,3-PD is added dropwise.Wherein, the molar ratio of three kinds of reactants is：
Dimethyl carbonate:1- alkenyl amylalcohols:1,3- propane diols=1:1.5:1.5, catalyst charge is the 0.2% of gross mass of feeding intake.
With the progress of reaction, Methanol product is constantly discharged out of system, and 20min cools after methanol no longer flows out, discharging.According to boiling
Point difference, vacuum distillation processing is carried out to product, separating by-products, obtains carbonic ester initiator (formula 2).
176g carbonic esters (formula 2) initiator and 0.5gKOH are added in high-pressure reactor.Water-tight equipment, nitrogen displacement 3
It is secondary.Stirring is opened, heating, 5g oxirane is passed through when temperature reaches 100 DEG C, after temperature rise pressure declines, continues to delay
It is slow to be passed through oxirane (EO 823g) raw material, controlling reaction temperature in 110~130 DEG C and kettle pressure in 0.3~0.5MPa.
After charging, after pressure gradually decreases down no longer decline in continuous 30 minutes in kettle, aging cooling discharge, low molecule amount is obtained
Polyether intermediate.
Take above-mentioned polyether intermediate 222g to be put into as initiator in high-pressure reactor, add 0.5gKOH, sealing is set
It is standby, nitrogen displacement 3 times.Stirring is opened, heating, 5g oxirane is passed through when temperature reaches 100 DEG C, when temperature is raised under pressure
After drop, continue to be slowly introducing oxirane (EO 778g) raw material, controlling reaction temperature pressure in 110~130 DEG C and kettle exists
0.3~0.5MPa.After charging, after pressure in kettle is gradually decreased down continuous 30 minutes and no longer declined, aging cooling discharge,
Obtaining polyethers JM-IV (formula 4), the test result of the number-average molecular weight of the ether, molecular weight distribution and double bond retention rate is shown in Table 1, its
Middle m=85.
Obtained polyethers is synthesized into water reducer with monomers such as methacrylic acids, step is as follows：In the reactor, 400g is added
Deionized water and 480g monomers A (atactic polyether of the present embodiment synthesis), 18.5g monomers B (acrylic acid), are heated with stirring to 80
DEG C, initiator (3.1 ammonium persulfates and 20g aqueous mixtures) and monomer C (2.2g methylpropene sodium sulfonates and 20g water is then added dropwise
Mixture), time for adding 2.5h, reaction time 3.5h, reaction are cooled to normal temperature after terminating, with mass concentration 30%
The NaOH aqueous solution adjusts pH value to neutrality, discharging, both obtains high-performance polycarboxylic acids water reducing agent product J SJ-IV, the correlation of the water reducer
The performance test results are shown in Table 2.
Embodiment 5
In the reactor for possessing condition of negative pressure, stirring is opened, adds dimethyl carbonate and sulfuric acid, it is to slowly warm up to 80~
It is 90 DEG C, double into reactor that 2- first propenyl and hydroquinones is added dropwise.Wherein, the molar ratio of three kinds of reactants is：Carbonic acid
Dimethyl ester:2- first propenyls:Hydroquinones=1:1.5:1.5, catalyst charge is the 0.2% of gross mass of feeding intake.With anti-
The progress answered, Methanol product are constantly discharged out of system, and 20min cools after methanol no longer flows out, discharging.According to boiling-point difference
It is different, vacuum distillation processing is carried out to product, separating by-products, obtains carbonic ester initiator (formula 5).
194g carbonic esters (formula 5) initiator and 1.5g NaOH are added in high-pressure reactor.Water-tight equipment, nitrogen displacement 3
It is secondary.Stirring is opened, heating, 6g oxirane raw material (EO) is passed through when temperature reaches 100 DEG C, when temperature rise pressure declines
Afterwards, continue to be slowly introducing remaining 700g EO, controlling reaction temperature in 110~130 DEG C and kettle pressure in 0.3~0.5MPa.EO
After charging, continue to be slowly introducing propylene oxide feedstock (PO) 100g into kettle, treat that pressure gradually decreases down continuous 30 minutes
After no longer declining, aging cooling discharge obtains block polyether JM-V (formula 6), the number-average molecular weight of the ether, molecular weight distribution and double
The test result of key retention rate is shown in Table 1, wherein m=18, n=2.
Obtained polyethers is synthesized into water reducer with monomers such as methacrylic acids, step is as follows：In the reactor, 70g is added
Deionized water and 110g monomers A (atactic polyether of the present embodiment synthesis), 18.5g monomers B (acrylic acid), are heated with stirring to 80
DEG C, initiator (3.1 ammonium persulfates and 20g aqueous mixtures) and monomer C (2.2g methylpropene sodium sulfonates and 20g water is then added dropwise
Mixture), time for adding 2.5h, reaction time 3.5h, reaction are cooled to normal temperature after terminating, with mass concentration 30%
The NaOH aqueous solution adjusts pH value to neutrality, discharging, both obtains high-performance polycarboxylic acids water reducing agent product J SJ-V, the correlation of the water reducer
The performance test results are shown in Table 2,3.
Embodiment 6
In the reactor for possessing condition of negative pressure, stirring is opened, adds dimethyl carbonate and sulfuric acid, it is to slowly warm up to 80~
It is 90 DEG C, double into reactor that metallyl alcohol and hydroquinones is added dropwise.Wherein, the molar ratio of three kinds of reactants is：Carbon
Dimethyl phthalate:Metallyl alcohol:Hydroquinones=1:1.5:1.5, catalyst charge is the 0.2% of gross mass of feeding intake.With
The progress of reaction, Methanol product is constantly discharged out of system, and 20min cools after methanol no longer flows out, discharging；According to boiling point
Difference, vacuum distillation processing is carried out to product, separating by-products, obtains carbonic ester initiator (formula 5).
194g carbonic esters (formula 5) initiator and 1.5g NaOH are added in high-pressure reactor.Water-tight equipment, nitrogen displacement 3
It is secondary.Stirring is opened, heating, 6g propylene oxide feedstocks (PO) are passed through when temperature reaches 100 DEG C, when temperature rise pressure declines
Afterwards, continue to be slowly introducing remaining 94g PO, controlling reaction temperature in 110~130 DEG C and kettle pressure in 0.3~0.5MPa.PO
After charging, continue to be slowly introducing propylene oxide feedstock (EO) 706g into kettle, treat that pressure gradually decreases down continuous 30 minutes
After no longer declining, aging cooling discharge obtains block polyether JM-VI (formula 7), the number-average molecular weight of the ether, molecular weight distribution and
The test result of double bond retention rate is shown in Table 1, wherein m=18, n=2.
Obtained block polyether is synthesized into water reducer with monomers such as methacrylic acids, step is as follows：In the reactor, add
70g deionized waters and 110g monomers A (atactic polyether of the present embodiment synthesis), 18.5g monomers B (acrylic acid), are heated with stirring to
80 DEG C, initiator (3.1 ammonium persulfates and 20g aqueous mixtures) and monomer C (2.2g methylpropene sodium sulfonates and 20g is then added dropwise
Aqueous mixtures), time for adding 2.5h, reaction time 3.5h, reaction are cooled to normal temperature after terminating, with mass concentration 30%
The NaOH aqueous solution adjusts pH value to neutrality, discharging, both obtains high-performance polycarboxylic acids water reducing agent product J SJ-VI, the correlation of the water reducer
The performance test results are shown in Table 2.
Embodiment 7
In the reactor for possessing condition of negative pressure, stirring is opened, dimethyl carbonate and sodium methoxide is added, is to slowly warm up to 80
It is~90 DEG C, double into reactor that butenol and ethylene glycol is added dropwise.Wherein, the molar ratio of three kinds of reactants is：Carbonic acid diformazan
Ester:Butenol:Ethylene glycol=1:1.5:1.5, catalyst charge is the 0.2% of gross mass of feeding intake.With the progress of reaction, production
Thing methanol is constantly discharged out of system, and 20min cools after methanol no longer flows out, discharging, and according to boiling point difference, product is carried out
Vacuum distillation is handled, and separating by-products, obtains carbonic ester initiator (formula 8).
Ormal weight 160g carbonic esters (formula 8) initiator and 0.3g KOH are added in high-pressure reactor.Water-tight equipment, nitrogen
Displacement 3 times.Stirring is opened, heating, 5g oxirane is passed through when temperature reaches 100 DEG C, after temperature rise pressure declines, after
It is continuous to be slowly introducing epoxyalkane ethane (EO 435g) raw material, controlling reaction temperature in 110~130 DEG C and kettle pressure 0.3~
0.5MPa.After charging, after pressure in kettle is gradually decreased down continuous 30 minutes and no longer declined, aging cooling discharge, obtain
Polyethers JM-VII (formula 9), the test result of the number-average molecular weight of the ether, molecular weight distribution and double bond retention rate are shown in Table 1, wherein m
=10.
Obtained polyethers is synthesized into water reducer with monomers such as methacrylic acids, step is as follows：In the reactor, 70g is added
Deionized water and 60g monomers A (atactic polyether of the present embodiment synthesis), 18.5g monomers B (acrylic acid), are heated with stirring to 80 DEG C,
Then initiator (3.1 ammonium persulfates and 20g aqueous mixtures) is added dropwise, and (2.2g methylpropene sodium sulfonates mix with 20g water with monomer C
Thing), time for adding 2.5h, reaction time 3.5h, reaction are cooled to normal temperature after terminating, with the NaOH water of mass concentration 30%
Solution adjusts pH value to neutrality, discharging, both obtains high-performance polycarboxylic acids water reducing agent product J SJ-VII, the correlated performance of the water reducer
Test result is shown in Table 2.
Embodiment 8
The polyethers JM-VI (formula 7, wherein n=2 that synthesize is added in embodiment 6 in high-pressure reactor；M=18) 111.5g
Initiator and 0.5g KOH.Water-tight equipment, nitrogen displacement 3 times.Stirring is opened, heating, 5g rings are passed through when temperature reaches 100 DEG C
Oxidative ethane, after temperature rise pressure declines, continue to be slowly introducing oxirane (EO 875g) raw material, controlling reaction temperature exists
110~130 DEG C with pressure in kettle in 0.3~0.5MPa.After charging, pressure gradually decreases down continuous 30 minutes no longer in kettle
After decline, aging cooling discharge obtains polyethers JM-VIII (formula 7), and number-average molecular weight, molecular weight distribution and the double bond of the ether are protected
The test result of rate is stayed to be shown in Table 1, wherein n=2, m=218.
Obtained polyethers is synthesized into water reducer with monomers such as methacrylic acids, step is as follows：In the reactor, 700g is added
Deionized water and 1000g monomers A (atactic polyether of the present embodiment synthesis), 18.5g monomers B (acrylic acid), are heated with stirring to 80
DEG C, initiator (3.1 ammonium persulfates and 20g aqueous mixtures) and monomer C (2.2g methylpropene sodium sulfonates and 20g water is then added dropwise
Mixture), time for adding 2.5h, reaction time 3.5h, reaction are cooled to normal temperature after terminating, with mass concentration 30%
The NaOH aqueous solution adjusts pH value to neutrality, discharging, both obtains high-performance polycarboxylic acids water reducing agent product J SJ-VIII, the phase of the water reducer
Close the performance test results and be shown in Table 2.
The alkenyl carbonic acid ester polyether index test result of table 1
| Sample | Hydroxyl value mg/g | Molecular weight | Molecular weight distribution index | Double bond retention rate % |
| JM-I | 47.3 | 1186 | 1.03 | 97.5 |
| JM-II | 23.5 | 2387 | 1.02 | 94.3 |
| JM-III | 51.6 | 1087 | 1.07 | 96.8 |
| JM-IV | 11.6 | 4836 | 1.09 | 94.5 |
| JM-V | 50.7 | 1106 | 1.05 | 95.7 |
| JM-VI | 50.3 | 1115 | 1.04 | 98.1 |
| JM-VII | 94.2 | 595 | 1.02 | 98.4 |
| JM-VIII | 5.73 | 9790 | 1.13 | 93.7 |
As it can be seen from table 1 the polyethers of the present invention, has narrower molecular weight distribution and higher double bond retention rate, produce
Product index is met the requirements, and guarantee is provided for synthesized high-performance water reducer.
Table 2 synthesizes water reducer the performance test results
Wherein, it is that the polyethers trade mark is OXAA- using the water reducer synthesized by commercially available allyl polyether to water reducer I
540；It is the water reducer synthesized by using the polyethers of the invention of patent 201210529380.9 to contrast water reducer II.
Table 2 judges the quality of water reducer dispersive property, the numerical value of initial slump degree by testing the slump of concrete
It is bigger, represent that the dispersive property of water reducer is better, and 1h slumps numerical value and initial slump degree are closer, illustrate that scattered retentivity is got over
It is good.The water reducer synthesized by polyethers of the present invention is can be seen that from the data of table 2, its dispersive property is superior to scattered retentivity
Contrast water reducer.
Table 3 synthesizes the anti-mud the performance test results of water reducer
| Project | Water reducer dosage/% | Initial flow degree (mm) |
| JSJ-I (is free of mud) | 0.3 | 220 |
| JSJ-I | 0.3 | 150 |
| JSJ-I | 0.34 | 225 |
| JSJ-II (is free of mud) | 0.3 | 225 |
| JSJ-II | 0.3 | 145 |
| JSJ-II | 0.35 | 220 |
| JSJ-V (is free of mud) | 0.3 | 210 |
| JSJ-V | 0.3 | 130 |
| JSJ-V | 0.38 | 210 |
| Contrast water reducer I (being free of mud) | 0.3 | 190 |
| Contrast water reducer I | 0.3 | 115 |
| Contrast water reducer I | 0.42 | 180 |
| Contrast water reducer II (being free of mud) | 0.3 | 200 |
| Contrast water reducer II | 0.3 | 120 |
| Contrast water reducer II | 0.43 | 200 |
Note：Cement clay content 0.02%.
Table 3 compares the quality of the anti-mud performance of water reducer by detecting under different condition flow of cement mortar, works as cement
In when containing foundry loam, the dispersive property of Water-reducing Admixtures To Cements can decline, and show the reduction of mortar fluidity numerical value；By to containing
The cement of mud, which improves water reducer dosage, can make up the loss of mortar fluidity.I.e. in identical water reducer dosage, containing mud and not
The ratio that mortar fluidity numerical value containing mud reduces is smaller, and its anti-mud is better；In addition, make to reach containing mud and the cement without mud
The increased water reducer of same mortar fluidity institute is fewer, it was demonstrated that its anti-mud is better.It can be seen that from the data of table 3：By upper
Contrasted of both stating, the anti-mud performance of water reducer in the embodiment of the present invention is better than contrast water reducer.
Unless limited otherwise, term used herein is the implication that those skilled in the art are generally understood that.
Embodiment described in the invention is not used to limit the scope of the invention merely for exemplary purpose,
Those skilled in the art can make various other replacements, changes and improvements within the scope of the invention, thus, the invention is not restricted to
Above-mentioned embodiment, and be only defined by the claims.
Claims (8)
1. a kind of alkenyl carbonic acid ester polyether, there is following structure：
Wherein, R1For H or C1~C3Alkyl；R2For C1~C5Alkylidene；R3For C3~C4Alkylidene, phenylene or benzal
Base；M is to include construction unit-CH2CH2O-、-CH(CH3)CH2O-、-CH2(CH3) one or more polyether chains in CHO-.
2. alkenyl carbonic acid ester polyether according to claim 1, it is homopolymer, random copolymer or block copolymer.
3. alkenyl carbonic acid ester polyether according to claim 1, its structure are：
Or
Wherein, m, n are integer, and 2≤m+n≤200.
4. alkenyl carbonic acid ester polyether according to any one of claim 1 to 3, its number-average molecular weight is 250~10000.
5. alkenyl carbonic acid ester polyether according to claim 4, its number-average molecular weight is 1000~5000.
6. a kind of preparation method of alkenyl carbonic acid ester polyether, including using alkenyl carbonic ester as initiator, carry out oxirane and/or
The ring-opening polymerization of expoxy propane, the alkenyl carbonic acid ester polyether is made；The structure of the alkenyl carbonic ester is as follows：
Wherein, R1For H or C1~C3Alkyl；R2For C1~C5Alkylidene；R3For C3~C4Alkylidene, phenylene or benzal
Base.
7. according to the method for claim 6, wherein the number-average molecular weight of the alkenyl carbonic acid ester polyether is 250~10000.
8. application of the alkenyl carbonic acid ester polyether in polycarboxylate water-reducer is prepared any one of claim 1 to 5.
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